IB-Chemistry LQ Answers-4

Chemistry for the IB Diploma – Answers
Answers to linking questions

THEME S
S1.1 Introduction to the particulate nature of matter
How do intermolecular forces influence the type of mixture that forms

between two substances?
This question links material from:
Themes S2.2 The covalent model
The general rule of thumb that can be used to decide if a solute will dissolve in a solvent is commonly
phrased as ‘like dissolves like’. This means that, in general, polar or ionic solutes will dissolve in polar
solvents, and non-polar solutes will generally dissolve in non-polar solvents.
For an ionic compound to dissolve in water, it is first necessary for the ionic bonding in the lattice and the
intermolecular attractions between water molecules to be broken. These are both endothermic processes,
meaning that energy is absorbed. Then new ion–dipole forces of attraction can be formed between the ions
and water molecules, which is an exothermic process, meaning that energy is released.
In general, an ionic compound might be expected to be very soluble in water if the energy released by the
hydration of its ions (hydration enthalpy) is similar to or larger than the energy required to break the forces
of attraction between the ions in the lattice (lattice enthalpy) and to separate the water molecules in the
solvent. There is an increase in entropy associated with dissolving, so if the dissolving is not accompanied by
a large endothermic enthalpy change, the ionic compound will be soluble. If this is not the case, then the
ionic compound is likely to be either sparingly soluble or insoluble and will form a heterogeneous mixture
when added to water. The energy required to separate the ions in an ionic lattice will generally be higher
when the cation and anion have higher charges and when they are similar in size to each other.
As a general rule, two liquids will mix if the process is energetically favourable and so it generally occurs
with a release of heat energy. Consider two liquids, X and Y. In order for the two liquids to mix, first the
intermolecular attractions between X molecules (X–X attractions) and Y molecules (Y–Y attractions) need
to be broken – these two processes both require heat to occur and are endothermic. Then new intermolecular
interactions can occur between X and Y molecules. Creation of X–Y attractions is an exothermic process.
When two liquids are mixed, one of three things can happen depending on the relative strength of the X–X,
Y–Y and X–Y attractions:
• The temperature decreases and there is little evidence of mixing since the X–X and Y–Y attractions
are stronger than the intermolecular forces between X and Y (X–Y attractions).
• The temperature stays approximately the same, indicating that the X–X, Y–Y and X–Y attractions
are similar in strength.
• The temperature rises because the intermolecular forces between X and Y are stronger than the X–X
and Y–Y attractions.
HL only
This simple approach is based on energetics and ignores entropy, which plays an important role in
determining the extent of solubility. The formation of a solution spreads molecules, atoms, or ions of one
type through a second substance, which generally increases the disorder and results in an increase in the
entropy of the system. Hence the entropy change almost always favours formation of a solution.
Chemistry for the IB Diploma Third edition © Hodder & Stoughton Limited 2023 1
Why are alloys generally considered to be mixtures, even though they

often contain metallic bonding?
Themes S2.3 The metallic model
Alloys can be formed by combining different metals (and sometimes small amounts of a non-metal) in
variable proportions. For example, brass is usually formed with 65% copper and 35% zinc; however, the
percentages may vary in different samples of brass. Compounds typically have a fixed ratio of one element
to another; because alloys can be formed from differing ratios of elements, they are usually considered to be
mixtures and not pure compounds. Furthermore, the mixed elements in alloys – for example, copper and zinc
in brass – are not combined chemically into a new compound. The alloy has physical properties intermediate
between those of the constituent metals, but the chemical properties of each element remain unaffected. For
example, when dilute acid is reacted with brass, the zinc reacts with the acid but the copper does not react.
Why are some changes of state endothermic and some exothermic?

Themes S2 Models of bonding and structure
R1.2 Energy cycles in reactions
Any change of state that takes you from particles with high potential energy to particles with less potential
energy is exothermic. An exothermic change of state involves the transfer of heat energy from the particles
of the chemicals to the surroundings and hence a rise in temperature. These exothermic changes of state –
condensation, freezing and deposition – all involve formation of new bonds or intermolecular forces.
Similarly, any change of state that takes you from particles with low potential energy to particles with higher
potential energy is endothermic. An endothermic change of state involves the transfer of heat energy to the
particles of the chemicals from the surroundings and hence a decrease in temperature. These endothermic
changes of state – melting, boiling and sublimation – all involve the breaking of bonds or intermolecular
forces.
Why are some substances solid while others are fluid under standard
conditions?
Themes S2.4 From models to materials
Two factors determine whether a substance is a solid or a fluid (liquid or
gas): the temperature and the interactions between the particles.
The chemical bonding or weaker intermolecular forces between particles
tend to bring the particles together, but the movement of the particles
tends to keep the particles apart.
If the average kinetic energy is greater than the energy required to
break the bonds or forces between the particles, a substance will not
condense to form a liquid or a solid. If the kinetic energy is less than the
energy stored in the bonds or forces, a liquid or solid will form.
Many molecular elements and compounds are liquids or gases at room
temperature because a small amount of heat energy is needed to Figure S1.A1 Molecules in
overcome the weak attractive forces between the molecules. Figure bromine liquid and gas
S1.A1 shows diatomic molecules of bromine, Br2, in a closed system.
The sample of bromine is at equilibrium and the bromine molecules exists in both the liquid and vapour
phase. Particles in the vapour phase collide with the surface of the liquid, become attracted to other liquid
particles and condense. At the same time, some energetic particles at the surface of the liquid break free from
these attractions and enter into the gas phase. These two processes occur at an equal rate. Changing the
temperature can alter the distribution of the particles between the different phases. Also, a different
substance than bromine would have a different distribution between the phases because the interactions
between the particles are of different strength.
What is the graphical distribution of kinetic energy values of particles in

a sample at a fixed temperature?
Themes R2.2 How fast? The rate of chemical change
The graphical distribution of kinetic energy values of particles in a sample at fixed temperature is known as
the Maxwell–Boltzmann distribution.
The kinetic molecular theory was developed independently by two physicists: Maxwell in Britain and
Boltzmann in Austria.
Figure S1.A2 shows the distribution of kinetic
energies for molecules of an ideal gas at two
different absolute temperatures. This result is
derived from theory and strongly supported by
experimental data.
Although at a specific time, the kinetic energy of a
specific gas particle is constantly changing as a
result of collisions, if the temperature is maintained
at a constant value, then the system of gas particles
has a fixed distribution of kinetic energy states and
its total kinetic energy is constant.
The area under the curve indicates the total number Figure S1.A2 The Maxwell–Boltzmann distribution of
kinetic energies of the molecules of a gas at two
of gas particles in the sample of gas (the system).
temperatures.
The highest peak gives the most probable value of
kinetic energy.
Because of the shape of the distribution, the mean kinetic energy lies slightly to the right of the most
probable value.
What must happen to particles for a chemical reaction to occur?

In a reaction of the type:
A+B→C
which occurs in a single elementary step, particles of reacting
substances A and B must collide with each other to form the
product C. There are only two types of collision: successful and
unsuccessful, as shown in Figure S1.A3.
In an unsuccessful collision, particles of A and bounce off each other
to remain as reactant particles A and B.
However, in a successful collision, particles of A and B collide and
form C. Collisions are only successful if the reacting particles contain
a minimum amount of combined kinetic energy known as the
activation energy.
When larger, more complex, reactants with reactive and unreactive
regions collide, collisions may also be unsuccessful because the
particles are not correctly oriented (leading to the inclusion of a steric
factor in calculations).
The rate of a chemical reaction depends on the number of successful
Figure S1.A3 Collision theory
collisions per second. If a change is made to increase the number of
successful collisions, such as an increase in the temperature of the
mixture, this will lead to an increase in the rate of the reaction.
S1.2 The nuclear atom
What determines the different chemical properties of atoms?

Themes S1.3 Electron configurations
Chemical reactions involve the movement of electrons, and the chemical reactivity of an atom is dependent
on its ability to attract or lose electrons relative to others. Atoms that possess a great driving force to lose or
gain electrons are the most reactive. Those which do not easily lose or gain electrons, such as the noble
gases, are unreactive.
The propensity for an atom to lose or gain an electron depends on the attractive force the atom’s valence
electrons experience from the atom’s nucleus. This attractive force is largely a result of the nuclear charge of
the atom, the shielding of the charge by other electrons in the atom, and the average distance between the
nucleus and valence electron.
The general trend going across a period (from left to right) is that it becomes less likely for atoms to lose
electrons, but more likely for atoms to gain electrons. Enthalpies of ionization and electron affinity quantify
this.
The chemical properties of atoms, other than those in group 18 (the noble gases), are not easily observed
because the atoms do not exist independent of one another. All atoms of elements not in group 18 will bond
with one another in some way. When individual atoms are formed, for example chlorine atoms formed by
the action of UV light on chlorine, Cl2, we find that the radicals made are very reactive and will strip
electrons from nearby electron paired molecules.
Elements in the same group of the periodic table have similar chemical properties. This can be ascribed to
the similar structure and bonding these elements possess, which in turn is a result of their similar electronic
configurations.
How does the atomic number relate to the position of an element in the
periodic table?
Themes S3.1 The periodic table
The atomic number of an atom determines the number of protons and, hence, the number of electrons in the
atom. Each atom has a unique electronic structure which determines its position in the periodic table (18
groups and 7 periods).
Consider a scandium atom with an atomic number of 21. The electron configuration of scandium is 1s2 2s2
2p6 3s2 3p6 3d1 4s2 3. In this notation, the digits, 1, 2, 3 and 4 refer to the electron shells (main energy levels)
in order from the nucleus, and the superscripts refer to the numbers of electrons. The highest filled sublevel
is 4s, so scandium is in period 4. Summing the electrons from (4s) to the end of the configuration to calculate
the total number of valence electrons, results in the following: [Ar] 3d1 4s2 3 (1 + 2 = 3). This element is in
group 3 and in period 4.
The modern periodic table has the 118 known chemical elements arranged according to their atomic
number:, that is, the number of protons in their nucleus. Earlier representations of the periodic table
organized the elements according to similarities in chemical properties, or in order of atomic mass (weight).
Examining the modern table indicates why ordering by relative atomic mass is problematic.
In general, the relative atomic mass increases as the periodic table is

traversed across and down but between there is a decrease between
element 52 (tellurium) and element 53 (iodine) as shown in Figure
S1.A5. Other examples can be found in the actinides and across the
seventh period.
The anomaly between tellurium and iodine was even known to
Dmitri Mendeleev (1834–1907) when he constructed his periodic
table in 1869. Despite the decrease in atomic mass between Te and I, Figure S1.A5 Atomic data for
he grouped tellurium with O, S and Se, and iodine with the halogens tellurium and iodine
based on similarities in their chemical behaviour.
A full understanding of this anomaly followed the
work of Henry Moseley (1887–1915) on the X-ray
spectra of the elements and the discovery of
isotopes by Francis Aston (1877–1945) during the
second decade of the twentieth century.
Moseley studied the X-rays emitted when atoms of
(mostly metallic) elements were bombarded by
high energy electrons. He discovered a simple
relationship (Figure S1.A6) between the frequency
of the X-rays emitted and the atomic (proton)
number (the square root of the X-ray frequency is
proportional to atomic number). From these results
Moseley suggested that one additional proton (and
therefore one electron) is added to the nucleus on
moving from one element to the next. Atomic
number is therefore a more fundamental property
than atomic mass.
Like Mendeleev before him, Moseley identified
gaps in his data and was able to predict the Figure S1.A6 Some of Moseley’s results for
the X-ray spectra of various metals
existence of (at the time) undiscovered elements
with atomic numbers 43 (technetium), 61
(promethium), 72 (hafnium) and 75 (rhenium). Moseley published his results in 1914, but was killed in the
First World War. Had he lived, he would have likely received a Nobel Prize for his work.
Shortly after World War I, Francis Aston built an instrument he called a mass spectrograph (now known as a
mass spectrometer). Using the mass spectrograph, Aston showed that neon (and, subsequently, other
elements) consists of atoms that have the same nuclear charge (proton number) but different nuclear masses
(due to differing numbers of neutrons). The relative atomic mass of an element is an average of the masses of
the isotopes, weighted according to the abundance of each isotope. Aston was awarded the 1922 Nobel Prize
for Chemistry.
Together with the work of Moseley, Aston’s results explain the “anomalous” order of Te and I in the
periodic table. Tellurium has a larger relative atomic mass because it occurs naturally with a higher
proportion of heavier isotopes than iodine.
How can isotope tracers provide evidence for a reaction mechanism?

Themes R3.4 Electron pair sharing reactions
Nature of Science Evidence
A chemical reaction may be followed by substituting a radioactive isotope of an element for the normal, non-
radioactive form.
By measuring the intensity of the radioactive decay due to the isotope, the concentration of the element may
be determined, even if it is present in very small concentrations. Radioactive isotopes used in ‘labelling’
ions, atoms and molecules during the study of chemical and biochemical processes are known as
radioisotope tracers. A similar approach can be used with non-radioactive isotopes and analysing samples
with mass spectrometry.
Isotope tracers have been used to investigate the mechanism of ester hydrolysis. This type of reaction
involves the reaction between an ester and water molecules to form an alcohol and carboxylic acid.
Using water molecules labelled with oxygen-18 atoms instead of the normal (more abundant) oxygen-16
atoms, it was possible to show which bond breaks in the ester during the hydrolysis reaction. Mass
spectrometry showed that the heavier oxygen-18 atoms from the water molecules ended up in the carboxylic
acid and not in the alcohol (Figure S1.A7).
Figure S1.A7 Use of labelling to investigate bond breaking during the hydrolysis of an ester
How does the fragmentation pattern of a compound in the mass

spectrometer help in the determination of its structure?
In the mass spectrometer, organic molecules will initially form a molecular ion which is the molecule that
has lost one electron to form a positive ion. For example, consider the molecule ethyl ethanoate:
CH3CO2CH2CH3 (g)  [CH3CO2CH2CH3]+ (g) + e−
This molecular ion can then undergo fragmentation via bond breaking within the molecule. One very simple
approach is to consider that each of the single bonds can be broken to form a positively charged fragment
that must contain at least one carbon atom. In each case an uncharged complementary fragment is also
produced, but this cannot be detected by the mass spectrometer.
For example:
[CH3CO2CH2CH3]+ (g)  [CH3CO]+ + OCH2CH3
No hydrogen ions, H+, are produced by fragmentation and double and triple bonds (that may be present in
organic molecules) are often not broken but retained in the fragments.
The mass spectrum obtained for ethyl ethanoate will show the molecular ion peak, in this case at a mass to
charge ratio (m/z) of 88, and the peaks due to the fragments formed. One fragment peak will have a m/z ratio
of 43, [CH3CO]+. An isomer of ethyl ethanoate, propyl methanoate, would have the same molecular ion
peak, but it would not have a fragment with a m/z ratio of 43. It is not possible for the molecular ion,
[HCO2CH2CH3CH3]+, to fragment and form [CH3CO]+.
In this way, fragmentation patterns can be useful when distinguishing between different isomers.
S1.3 Electron configurations
What qualitative and quantitative data can be collected from

instruments such as gas discharge tubes and prisms in the study of
emission spectra from gaseous elements and from light?
Inquiry processes Inquiry process 2: Processing data
A gas discharge tube contains electrodes surrounded by a gas within an insulating, heat-resistant container.
The tube generates light using an electric discharge (a spark). A typical discharge tube contains a gas (often a
noble gas) but other substances like mercury, an alkali metal or metal halide can be used if they are
vaporized during start-up to form a low-pressure gas.
When a voltage is applied across the electrodes, some of the gas near the anode is ionized by the strong
electric field to form positive ions. The electrons released are able to flow from the anode to the cathode
through the external circuit, and the positive ions are accelerated towards the cathode by the electric field.
After travelling a short distance, the cations collide with neutral gas atoms. These transfer electrons to the
ions, become cations themselves (with the original cations now becoming neutral atoms again) and
accelerate towards the cathode. As the transferred electrons make transitions to lower energy levels, energy
is released in the form of photons of characteristic frequencies given by the equation E = hf.
Light that falls within the visible part of the spectrum will cause the discharge tube to glow with a
characteristic colour such as the bright orange-yellow of a sodium street light. Flame tests use these
distinctive colours to qualitatively identify the element.
A spectroscope
containing a prism or
diffraction grating
will separate the
wavelengths of light
from a source.
Figure S1.A9 The emission or line spectrum of sodium vapour
Figure S1.A9 shows
the emission spectrum produced when light from a sodium discharge tube is viewed using such an
instrument.
Quantitative measurement of the frequencies
emitted across the full electromagnetic spectrum
can be used to infer the existence of energy levels
within the atoms and deduce their respective
energies. The energy levels for hydrogen,
calculated from lines in the Lyman series, are
shown in Figure S1.A10.
The lines in the Lyman series get closer together at
higher frequencies, approaching the convergence
limit. This limit corresponds to the transition of an
electron from n = ∞ to n = 1 and, therefore, the
associated energy is equal to the ionization energy
of hydrogen.
Figure S1.A10 Some of the energy levels

of the hydrogen atom
The convergence limit can be estimated by plotting a graph of ∆f

(change in frequency between neighbouring transitions) against f and
extrapolating the resulting curve to the x-axis to read off the
frequency of the convergence limit (Figure S1.A11).
How do emission spectra provide evidence

for the existence of different elements?
Themes S1.2 The nuclear atom
Nature of Science Evidence
Since the energy levels of the atoms of an element are dependent on Figure S1.A11 Estimating
the atomic number of the element, each element produces a unique ionization energy by extrapolation
emission spectrum that can serve as a ‘fingerprint’.
When the technique of spectroscopy was first developed by
scientists in the nineteenth century, they were able to use the spectra measured for elements in the laboratory
to identify chemical elements present in the Sun, due to the presence of lines of identical frequency in the
solar absorption spectrum.
Similarly, lines that were observed in the solar absorption spectrum that were not possessed by any elements
measured in laboratories up to that time (see Figure S1.A12) led scientists to propose the existence of an
undiscovered element, helium (named after the Greek Sun god, Helios).
Figure S1.A12 The emission or line spectrum of helium
How does an element's highest main energy level relate to its period
number in the periodic table?
The highest main energy level occupied by electrons in an element has a principal quantum number equal to
the number of the period in the periodic table in which the element is located. For example: hydrogen (1s1)
and helium (1s2) are both in period 1, both have electrons in the first shell (main energy level, n = 1); boron
(1s2 2s2 2p1) is in period 2 and its valence electrons are in the second shell (n = 2).
What is the relationship between energy sublevels and the block nature
of the periodic table?
The periodic table is divided into four main blocks (s, p, d and f). The electron configuration of an element
can, in many cases, be determined by simple inspection of the element’s position relative to the s, p, d and f
blocks.
The s-block consists of Groups 1 and 2, the p-block of groups 13 to 18, and the d-block of groups 3 to 12.
The f-block elements (lanthanides and actinides) are usually displayed separately at the bottom of the table
as shown in Figure S1.A13.
Figure S1.A13 Long form of the periodic table showing the s, p, d and f blocks
An element in the s-block or p-block has its valence electrons in an s- or p-sublevel respectively, for
example, Na 1s2 2s2 2p6 3s1 in group 1 has its valence electron in an s-sublevel (3s), and Br 1s2 2s2 2p6 3s2 3p6
3d10 4s2 4p5 in group 17 has its least tightly bound valence electrons in a p-sublevel (4p).
Elements in the d-block or f-block possess one or more electrons in a d- or f-sublevel respectively, however
these are never the outermost electrons (the highest energy electrons that are first to be lost upon ionization),
as the d- and f-block elements possess s-sublevel (and sometimes d-sublevel) electrons in orbitals of higher
principal quantum number, for example, V: [Ar]3d3 4s2; Ce: [Xe]4f1 5d1 6s2; Am: [Rn]5f7 7s2.
How does the trend in IE values across a period and down a group
explain the trends in properties of metals and non-metals?
The metals are on the left side of the periodic table and the non-metals are on the right. Metallic chemical
properties decrease across a period and non-metallic properties increase (Table S1.A2).
Table S1.A2 Period 3 elements
Group Symbol Name Classification First IE / kJ mol−1

1 Na sodium metal 496
2 Mg magnesium metal 738
13 Al aluminium metal 578
14 Si silicon metalloid 787
15 P phosphorus non-metal 1012
16 S sulfur non-metal 1000
17 Cl chlorine non-metal 1251
18 Ar argon non-metal 1520
The decrease in metallic characteristics corresponds with a general increase in first ionization energies.
Looking at groups within the periodic table, although there is a trend in first ionization energies in groups 1
and 2 (which can be used to explain chemical reactivity), there is no clear trend if you look at the thermal
and electrical conductivities of the alkali metals and alkaline earth metals.
The trend of increasing metallic chemical properties is shown clearly when going down groups 14 and 15
(Table S1.A3), both of which have a mixture of metals, metalloids and non-metals. This increasing metallic
character is accompanied by decreasing first ionization energies. There is generally an increase in electrical
conductivity down the group. However, graphite is a relatively good conductor due to the presence of
delocalized electrons.
Table S1.A3 First ionization energies of group 14 and 15 elements
Group 14 element First IE / kJ mol−1 Group 15 element First IE /kJ mol−1

carbon (non-metal) 1086 nitrogen (non-metal) 1402
silicon (metalloid) 787 phosphorus (non-metal) 1012
germanium (metalloid) 762 arsenic (metalloid) 944
tin (metal) 709 antimony (metalloid) 831
lead (metal) 716 bismuth (metal) 703
Why are log scales useful when discussing [H+] and ionization
energies?
Themes R3.1 Proton transfer reactions
Tools Tool 3 Mathematics
Nature of Science Measurement
Logarithms are a powerful way to make a set of numbers that cover many orders of magnitude more
manageable, so logarithmic scales are useful for presenting data that covers a large range of values.
The table below shows how taking the logarithm of the hydrogen ion concentration reduces the range of
numbers being dealt with. If values for the molar concentration of hydrogen ions range from 1 to
0.000 000 000 000 01 mol dm-3, the pH values will range from 0 to 14.
Table S1.A4 Hydrogen ion concentration and pH
pH 0 1 7 13 14
[H (aq)] / mol dm −3
+
1 10 −1 10 −7 10 −13 10 −14
Figure S1.A14 shows the successive
ionization energies of silicon; that is, the
energies required to remove all electrons
from a gaseous silicon atom starting from
the valence shell (third main energy level) to
the inner first shell (first main energy level).
Plotting the graph as log10 (ionisation
energy) against number of electrons removed
makes the data easier to interpret.
The first increase shown in the graph, from
the removal of the fourth electron to that of
the fifth, is due to a change in the energy
level from which the electron is taken: the
fourth electron is removed from the valence Figure S1.A14 Successive ionization energies for silicon,
shell (n = 3) and the fifth electron is from the plotted using a log scale
second shell, closer to the nucleus. There are
relatively small increases when the sublevel changes.
Below is the same information plotted on a linear scale. Because the ionization energies become very large,
the trend in the lower energy (earlier) ionization energies is not easy to observe.
How do patterns of successive IEs of transition elements help to explain

the variable oxidation states of these elements?
A graph of ionization energies against proton number for the first row of the d block containing transition
elements (Figure S1.A16) shows three main features.
Figure S1.A16 Ionization energies of the 3d-block elements (calcium from the s block is
included for comparison)
• The first and second ionization energies show a small overall increase across the d block.
• The second ionization energies are only slightly higher than the first.
• The third ionization energies are significantly higher and show a characteristic d-sublevel pattern.
The first ionization energies involve the removal of a 4s electron. This is outside the 3d sublevel and is
partially shielded by it. As the nuclear charge increases across the block due to additional protons, the
additional 3d electrons shield the effect of the increasing nuclear charge so that the 4s electron experiences
only a small additional electrostatic attraction.
The same effect is shown by the second ionization energies, with the exception of those for chromium ([Ar]
3d5 4s1) and copper ([Ar] 3d10 4s1); these have higher second ionization energies because the second electron
removed is a 3d electron, which does experience the increased nuclear charge.
The third ionization energies involve the removal of a 3d electron. The pattern of five IE values steadily
rising, followed by a drop and then five more steadily rising, mirrors the ionization energies involving the
removal of 2p electrons from atoms as the second period is crossed.
The decrease from manganese ([Ar] 3d5 4s2) to iron ([Ar] 3d6 4s2) occurs because the formation of the
iron(III) ion involves the removal of an electron from a 3d orbital containing two electrons of opposite spin;
this electron is more easily removed because it is repelled by the other 3d electron in the same orbital. (see
Figure S1.A17).
The number of electrons available for bonding in an atom determines its oxidation state. In
transition elements, the 4s and 3d electrons are available for removal to form cations (for example,
Mn2+ (3d3) or sharing to form oxyanions (for example, MnO4– and CrO42–) which explains why
transition elements have variable oxidation states. A common oxidation state is +2 which is usually
formed when the two 4s electrons are lost. Chromium, iron and cobalt form M3+ cations as their
third ionization energies are relatively low.
There is only a small energy gap between

the 3d orbital and the 4s orbital in the
transition elements. The 4s electrons are
lost first followed by the 3d electrons. In
transition metals, the ionization energy
required to remove the third electron – the
first in the 3d sublevel – is not significantly
greater than the ionization energies
required to remove the two 4s electrons.
Chromium and manganese show their
highest oxidation states of +7 and +6 in
MnO4– and CrO42–. In these oxyanions, the
oxidation states of the metals are equal to
Figure S1.A17 The electronic configurations of
the sum of the numbers of 3d and 4s manganese and iron atoms and their dipositive and
electrons; this shows that all of these tripositive cations.
electrons are used in the covalent bonding.
Why are data on successive ionization energies of a transition element

often not useful in assigning the group number of the element?
Table S1.A7 shows that the pattern in the successive ionization energies of the fourth period d-block
elements conforms to what might be expected in that the largest jump in IE occurs once the ion has become
isoelectronic with argon, that is, after the 4s and 3d electrons have all been removed. For example,
manganese has a [Ar] 3d54s2 configuration, and there is a large jump in ionization energy between the
seventh and eighth IE because Mn7+ is isoelectronic with argon. We can therefore correctly infer from the
data in the table that manganese is in Group 7.
Table S1.A7 Successive ionization energies for d-block elements
Ionization number IE / kJ mol−1

Sc Ti V Cr Mn Fe Co Ni Cu Zn
1 633 659 651 653 717 762 760 737 745 906
2 1235 1310 1412 1591 1509 1563 1648 1753 1958 1733
3 2389 2653 2828 2987 3249 2957 3232 3395 3555 3833
4 7091 4175 4507 4743 4941 5298 4947 5299 5536 5748
5 9581 6299 6702 6987 7236 7671 7339 7700 7970
6 12360 8745 9224 9551 9842 10420 9938 10420
7 15470 11500 12060 12440 12740 13410 12920
8 18860 14580 15230 15630 16020 16780
9 22540 17960 18640 19100 19590
10 26570 21680 22400 22960
11 30830 25600 26480
12 35410 29990
13 40290
However, when the identity of an element is unknown, IE data must be interpreted with caution. For
example, compare the first five IEs of titanium ([Ar]3d24s2) with the first five IEs of silicon ([Ne]3s23p2)
which are 787, 1577, 3232, 4356, and 16 091 kJ mol−1, respectively.
For atoms of both elements there is a large jump in ionization energy between the fourth and fifth IEs
because both Ti4+ and Si4+ are isoelectronic with the nearest noble gas (argon and neon, respectively). For
similar reasons, using IE data alone it is possible to confuse any elements possessing a dn configuration with
those possessing a pn configuration (where n = 1 … 6).
Comparison of first IEs shows that whilst, in general, there is an increasing trend in first ionization energy
across a period, there are specific instances that do not conform to the general increase (note the dips
between Ti and V, Fe and Co, Co and Ni).
Therefore, given a list of only first (or second, third, etc.) IEs for transition elements selected from the same
period, it would not be possible to list them in order of their group numbers without prior knowledge of the
detailed trend.
S1.4 Models of the particulate nature of matter
Atoms increase in mass as groups are descended in the periodic table.

What properties might be related to this trend?
Atoms increase in mass as a group is descended in the periodic table mainly due to the increase in the
number of protons and neutrons in the nucleus of the atoms.
Since there is a close (but not perfect) correlation between atomic number and relative atomic mass, many
periodic properties correlate with increasing mass including electronegativity, ionization energy, electron
affinity, atomic radii and ionic radii.
However, these properties are more a consequence of the increasing charge of the nucleus than of increasing
mass, so the observed correlations do not have a direct causal link. Consider, for example, the data in Table
S1.A8.
Table S1.A8 Melting points for the alkali metals and the diatomic halogens
Element Melting point / °C Element Melting point / °C

Li 180.50 F −219.7
Na 97.79 Cl −101.5
K 63.38 Br −7.1
Rb 39.30 I 113.7
Cs 28.44 At 301.8
The group 1 metals show a negative correlation between melting point and mass, whereas the halogens show
a positive correlation between melting point and mass. Once again, the correlations do not confirm a direct
causal link between melting point and mass.
The increase in melting point of the halogens is due to the increase in the strength of the London forces
between the molecules as the size of their electron clouds grows.
The observed decrease in the melting points of the alkali metals is due to the decrease in charge density of
the cations as the group is descended. All group 1 cations have a +1 charge, but the ions increase in volume
down the group as the number of electron shells increases, and this reduces the strength of the metallic bonds
within the metal.
This is not to say that mass has no influence on melting or boiling point, but the effect is very small. For
example, H2 (diprotium) has a boiling point of 20.4 K and D2 (dideuterium) boils at 23.5 K. The mass
increase due to the additional neutron in each hydrogen nucleus is more or less 100% but it only leads to a
15% increase in boiling point, and this is a fairly extreme case.
Consider also the boiling points of H2O (100°C) and NH3 (−33.3°C). The two molecules have nearly
identical molar masses but very different boiling points. It is therefore clear that intermolecular forces, which
are electrostatic in nature, have a much greater impact on boiling point than mass.
Properties that can be expected to depend directly on the trend of increasing mass when descending a group
𝑚𝑚 (g)
are those that are directly affected by mass such as molar volume and density, 𝜌𝜌 (g cm−3 ) = 𝑉𝑉 (cm3 ) .
How can molar masses be used with chemical equations to determine

the masses of the products of a reaction?
Themes R2.1 How much? The amount of chemical change
If you start with a known mass of one substance in a chemical reaction, you can calculate the corresponding
masses of other substances in the reaction by following these three steps:
1 Convert the known mass (g) into an amount (mol), using the substance’s molar mass.
2 Use the balanced chemical equation to work out the amount (mol) of other substances in the
reaction.
3 Convert this amount to the corresponding mass.
Applying these steps to determine the mass of magnesium chloride that will be formed when 3.76 g of
magnesium is reacted with an excess of dilute hydrochloric acid:
1 amount of magnesium = (3.76 g / 24.31 g mol−1) = 0.155 mol
2 Mg (s) + 2HCl (aq) → MgCl2 (aq) + H2 (g)
1 mol Mg → 1 mol MgCl2
so 0.155 mol Mg → 0.155 mol MgCl2
3 mass of magnesium chloride = (0.155 mol × 95.21 g mol−1) = 14.8 g
What is the importance of approximation in the determination of an

empirical formula?
Themes S3.2 Functional groups
Tools Tool 3 Mathematics
Nature of Science Measurement
When you carry out an empirical formula calculation based on mass, you should not round up the figures
until the end of the calculation. For example, ammonium hydroxide, NH4OH, and hydroxylamine, NH2OH,
have a similar chemical composition and if the data is rounded too soon, the wrong formula may be obtained.
Consider the empirical formula of a compound with the following composition: carbon 39.13%, oxygen
52.17% and hydrogen 8.700%.
C O H
amount in 100 g 39.13 g / 12.01 g mol−1 52.17 g / 16.00 g mol−1 8.700 g / 1.01 g mol−1
= 3.26 mol = 3.26 mol = 8.61 mol
Dividing by the smallest amount of atoms:
mole ratio 1 1 2.64
Dividing by the smallest amount has not resulted in an integer ratio and we cannot write the empirical
formula as C1H2.66O1.
It is therefore necessary to examine the numbers and see if there is a (small) number by which they can be
multiplied which would leave them all as integers (or numbers very close to integers). In this example, 0.64
is near to ⅔ so multiplying by 3 gives C3H8O3 as the empirical formula.
How can experimental data on mass changes in combustion reactions

be used to derive empirical formulas?
Tools Tool 1 Measuring variables
Combustion analysis is used to determine the empirical and molecular formulas of hydrocarbons by
determining the amounts of carbon and hydrogen present in the compound.
This is done by burning a measured mass of the hydrocarbon in excess oxygen using the apparatus shown in
Figure S1.A17. Suction from a water pump ensures the gases produced are pulled slowly through the U-
tubes. Anhydrous calcium chloride (or anhydrous copper(II) sulfate) absorbs the water produced, and soda
lime absorbs the carbon dioxide formed allowing the mass of each product to be found.
Figure S1.A17 Using combustion to determine the formula of a hydrocarbon
The required formula can then be determined by comparing with the general equation for the combustion of
a hydrocarbon:
𝑦𝑦
CxHy + (x + y/4) O2 → xCO2 + H2O
2
What are the considerations in the choice of glassware used in

preparing a standard solution and a serial dilution?
Tools Tool 1 Applying techniques
A standard solution is a solution containing a precisely known concentration of a substance. Because of the
requirement for high precision, standard solutions are prepared using volumetric flasks. The size of flask
used depends on the total volume of solution that is required.
Solids should be weighed using high precision digital scales and liquids either weighed in the same way or
the volume measured by pipette, as appropriate.
A serial dilution is a series of sequential dilutions that are carried out in order to prepare solutions of a range
of accurately known concentrations. This may be necessary to, for example, obtain a calibration curve for a
colorimetric analysis, or prepare a reagent at different concentrations when the reagent concentration is the
independent variable in an investigation.
If high precision is required, volumetric flasks and pipettes should be used in preparing the dilutions.
How can a calibration curve be used to determine the concentration of a

solution?
Inquiry processes Inquiry process 2 Collecting data
Figure S1.A18 shows that purple coloured potassium manganate(VII)
solutions of different concentrations absorb more light the more
concentrated they are. Spectroscopic techniques can be used to measure
the absorbance of light at one wavelength and determine the
concentrations of solutions.
The basis for the approach is the Beer–Lambert law: for a fixed path Figure S1.A18 Potassium manganate
length (l), the absorbance (A) is directly proportional to concentration (VII) solutions of different concentration
(c), as shown in Figure S1.A19, provided the coloured solution is dilute.
𝐴𝐴 = 𝜀𝜀𝜀𝜀𝜀𝜀
where ε is the molar absorption coefficient.
A calibration line is prepared covering the concentration range
appropriate for study. The absorbance of a sample solution can then be
measured and its concentration obtained from the graph by
interpolation.
Avogadro’s law applies to ideal gases. Under

what conditions might the behaviour of a real Figure S1.A19 Beer–Lambert law
gas deviate most from an ideal gas?

Themes S1.5 ideal gases
Molecular kinetic theory assumes that particles of an ideal gas do not produce any forces on each other and
that they have a negligible volume compared with that of the container. However, deviations from ideal
behaviour occur under certain conditions: the pressure, volume and temperature vary in ways that are not
accurately described by the gas laws.
At high pressures, the amount of empty space between the molecules is
reduced and the volume of the gas molecules themselves becomes
significant relative to the total volume occupied by the gas. The gas,
therefore, is less compressible and, although its volume continues to
decrease with increasing pressure, the decrease is no longer modelled by
Boyle’s law, which states that pressure and volume of a gas (at constant
temperature) are inversely proportional.
At higher pressures, intermolecular attraction also becomes significant
and brings the molecules a little closer together, decreasing the volume.
If the volume is constant, it instead decreases the pressure slightly.
Figure S1.A20 shows how the behaviour of a real gas at constant
temperature deviates from ideal gas behaviour on a pressure (P) versus Figure S1.A20 PV curves for an
volume (V) graph. At high pressure, the measured volume of the gas is ideal gas and a real gas
more than that calculated from Boyle’s law. At low pressure, the
calculated and the measured volumes approach each other.
S1.5 Ideal gases
Under comparable conditions, why do some gases deviate more from

ideal behaviour than others?
The strengths of intermolecular and interatomic forces in gases are typically small and not significant at low
pressure because the molecules or atoms are too far apart to experience the attractive force which decreases
rapidly with distance. They are also not significant at high temperatures because the molecules have large
amounts of kinetic energy and when two particles with high kinetic energies collide, a weak attraction
between them hardly affects the collision. Thus, under conditions of low pressure and high temperatures, the
collisions can be regarded as essentially elastic with total kinetic energy conserved.
However, at low temperatures and high pressure, the strengths of attractive forces between atoms and
molecules in the gas phase becomes significant and deviation from ideal behaviour occurs. Under these
conditions, molecules or atoms of the gas spend more time interacting with each other and less time colliding
with the walls of the container, making the actual pressure less than that predicted by the ideal gas law.
This effect is maximized for gas molecules which are significantly polar and form strong intermolecular
forces between their molecules. Very polar molecules will interact strongly without undergoing elastic
collisions, especially if they can hydrogen-bond.
The other factor that varies between gases is the size or volume of the gas atoms or molecules. This matters
because the other key assumption of the molecular kinetic theory describing ideal gases is that the total
volume of all the particles is negligible in comparison to that of the container. In gases with large molecules
or atoms (those with a large value of molar mass), the particles will not have a negligible volume and hence
the gas will deviate from ideal behaviour.
For an ideal gas,
PV / RT = n
Therefore, for 1 mole of an ideal gas,
PV / RT = 1.
The combined effects of particle size of volume and
intermolecular or interatomic forces can be studied
by examining a plot of PV / RT versus P for 1 mole
of noble gases (Figure S1.A21).
For real gases, PV / RT deviates from 1, but the
deviations are not uniform. The combined effects of
the volume or size of gas particles and the
interactions between the particle cause each real gas
to deviate from ideal behaviour in a slightly different
way.
Large negative deviations occur when the effect of
intermolecular forces on decreasing the pressure Figure S1.A21 Real versus ideal behaviour for gases at
(relative to an ideal gas) is far greater than the effect 5000 K, where for 1 mole of an ideal gas, PV / RT =1
of particle size on increasing the volume.
How can the ideal gas law be used to calculate the molar mass of a gas
from experimental data?
Themes Tool 1 Experimental techniques
Inquiry processes Inquiry process 3 Concluding and evaluating
Simple apparatus to measure the molar mass of gas in the laboratory is shown in Figure S1.A22. The flask
used to contain the gas must be of known volume. If it is not printed on the flask, the volume can be found
by filling it with water and then pouring the water into a measuring cylinder. The flask should then be dried
in an oven.
Figure S1.A22 Determining the molar mass of a gas
The mass of the flask containing air is at ambient pressure and temperature is measured. The mass of air can
be calculated using m = ρ × V and a value for the density of air at the required temperature and pressure from
a data table or other reliable source. This is then used to calculate the mass of the flask alone.
The flask is then filled with the gas of interest, again at ambient pressure and temperature and the mass
measured. The mass of this gas can be determined by subtracting the calculated mass of the flask from the
new measurement.
Under conditions of constant temperature and pressure, the ideal gas equation, PV = nRT, reduces to V ∝ n.
Since, for a given substance, n ∝ m, V ∝ m. We can use this, along with the molar volume at the relevant
temperature and pressure (again available from relevant literature) to calculate the molar mass.
The results below were obtained using ethane, C2H6, at a temperature of 25.0 °C and standard pressure:
volume of flask = 242.5 cm3
mass of flask + air = 58.260 g
mass of flask + ethane = 58.285 g
A data book shows that, at standard pressure and 25.0 °C, the density of air = 1.205 × 10−3 g cm−3
so mass of air = density of air × volume of air = 1.205 × 10−3 g cm−3 × 242.5 cm3 = 0.292 g
and mass of flask = (mass of flask + air) – (mass of air) = (58.260 g – 0.292 g) = 57.97 g
so mass of ethane = (mass of flask + ethane) – (mass of flask) = (58.285 g – 57.97 g) = 0.315 g
The moles of ethane present in the flask is calculated using the ideal gas equation:
𝑃𝑃𝑃𝑃 101,000×242.5×10−6
𝑛𝑛 = = = 9.89 × 10−3 mol
𝑅𝑅𝑅𝑅 8.31×298
The molar mass can be found by dividing the mass by the amount of moles:
0.315 g
𝑀𝑀 = = 31.8 g mol−1.
9.89×10−3 mol
The literature value for the molar mass of ethane is 30.08 g mol−1, and hence the % error of the experiment
is:
31.8 – 30.08
× 100 = 5.7%
30.08
Graphs can be presented as sketches or as accurately plotted data

points. What are the advantages and limitations of each representation?
Tools Tool 2 Applying technology to process data
Tool 3 Graphing
Nature of Science Patterns and trends
A sketch graph is a graph that lacks a numerical scale on the axes and
does not display data points. A sketch graph is useful since it can show
a mathematical function, such as an exponential function, or the
relationship between variables.
Figure S1.A23 shows a linear relationship between the volume of the Figure S1.A23 Relationship
gas (dependent variable) and absolute temperature (independent between volume and temperature
at different pressures
variable) at constant pressure. A horizontal line on the graph at constant
volume passes through P1 then P2 then P3, suggesting that pressure is
proportional to temperature at constant volume.
The sketch graph can show trends and the nature of a mathematical relationship but the absence of axes with
a numerical scale and data points means that numerical data cannot be derived from it.
The plotting of graphs with labelled and scaled axes showing data points is an essential part of the
presentation and analysis of quantitative empirical scientific data. They can be used to establish a numerical
relationship between the two variables. Determining the gradient and the intercept of a straight-line graph is
often helpful and may give useful chemical information, especially in the context of kinetics.
For example, every linear graph can be represented by the equation:
y = mx + c
where m is the gradient and c is the y-intercept.
Graphs with scaled axes can also be used to carry out interpolation (determining data points between
measurements) and extrapolation (estimating values outside the range of data values). For a small number of
graphs in chemistry, the area under the graph may be a useful quantity.
S2.1 The ionic model
Why is the formation of an ionic compound from its elements a redox

reaction?
Themes R3.2 Electron transfer reactions
Reduction–oxidation or redox reactions are those in which electrons transfer from one reactant to the other.
Oxidation is the loss of electrons and reduction is the gain of electrons.
Consider the synthesis of calcium fluoride from calcium and fluorine (Figure S2.A1).
Figure S2.A1 Formation of a calcium fluoride formula unit via electron transfer
Atoms of the metal, which have a tendency to lose electrons and form cations, react with atoms of the non-
metal, which have a tendency to gain electrons and form anions. The calcium atom transfers one electron to
each of two fluorine atoms. The resulting calcium and fluoride ions then form a giant lattice containing
calcium and fluoride ions in a 1 : 2 ratio. Calcium is a reducing agent, since it loses electrons, and fluorine is
an oxidizing agent, since it gains electrons.
Redox reactions can also be described in terms of oxidation states. An oxidation state is a signed number
given to each atom in a compound based on electronegativity. Atoms in elements have an oxidation state of
zero. The oxidation state of an atom in a compound is the charge it would have if all shared electrons were
given to the most electronegative atom; that is, the atom with the greatest attraction for those electrons.
Calcium has an electronegativity of 1.0 and fluorine has an electronegativity of 4.0, which shows that
fluorine has a much higher affinity for electrons than calcium. Hence, the Ca2+ ions are assigned an oxidation
state of +2 and F− ions have an oxidation state of −1. An increase in oxidation state during a reaction is
oxidation and a decrease in oxidation state during a reaction is reduction.
Polyatomic anions are conjugate bases of common acids. What is the

relationship between their stability and the conjugate acid’s
dissociation constant, Ka?
Weak acids react reversibly with water to form hydronium ions and anions as shown in the generalized
equation below:
HA (aq) + H2O (l) ⇌ H3O+ (aq) + A− (aq)
HA is a Brønsted–Lowry acid since, in the forward reaction, it loses a proton, H+, and forms an anion, A−
(the conjugate base). The water molecule acts as a Brønsted–Lowry base in the forward direction since it
accepts the proton to form the hydronium ion, H3O+. HA is a monoprotic acid since each molecule loses one
proton to form one hydronium ion.
Most acids are weak but their relative strength is determined by the extent to which the proton is lost at
equilibrium. This is measured by the acid dissociation constant, Ka, which is an equilibrium constant. The
stronger the acid, the higher the value of Ka.
Solids and pure liquids (in this case, water acting as a solvent with constant concentration) are not included
in equilibrium expressions so the equilibrium expression for a weak monoprotic acid is:
[H3 O+ ] × [A− ]
𝐾𝐾𝑎𝑎 =
[HA]
In the backward reaction, the hydronium ion loses a proton, acting as an acid, and the anion, A−, accepts the
proton, acting as a base:
H3O+ (aq) + A− (aq) → HA (aq) + H2O (l)
The base and acid on the right-hand side are the conjugates of the acid and base on the left-hand side. The
conjugate base is simply the acid minus its proton. Any anion, whether simple or polyatomic, can be
regarded as the conjugate base of a weak acid. A conjugate base can accept a proton from a hydronium
cation to reform the acid molecule, HA.
The degree to which the reaction above favours the forward direction depends on the strength of the
attraction between H3O+ and the conjugate base, A−:
• If the attraction between H3O+ and A− is weak, then A− is stable, the forward reaction is favoured and
the acid is strong; Ka has a high value.
• If the attraction between H3O+ and A− is strong, then A− is less stable, the reaction favours the
backward direction and the acid is weak; Ka has a low value.
A stable conjugate base is not very basic.
The more stable the conjugate base, the stronger the acid. A very strong acid has a very weak conjugate base
and a very weak acid has a very strong conjugate base but the conjugate base of a weak acid is still a weak
base). (Figure S2.A2).
High values of Ka indicate a stable anion whilst low values of Ka indicate an unstable anion.
Figure S2.A2 Relationship between strengths of an acid

and its conjugate base
How does the position of an element in the periodic table relate to the
charge of its ion(s)?
The elements in groups 1, 2 and 13 have only 1, 2 or 3 electrons in their outer shell. These elements at the
beginning of a period, other than boron (B), lose electrons to form positive ions (cations). The resulting
simple ions obey the octet rule and have an electron arrangement like the noble gas at the end of the previous
period. For example:
Na → Na+ + e−
Mg → Mg2+ + 2e−
Al → Al3+ + 3e−
Na+, Mg2+ and Al3+ are isoelectronic species: they all have the same electronic structure as neon, Ne, that is:
2,8 or 1s2 2s2 2p6.
The elements in groups 15, 16 and 17 have 5, 6 or 7 electrons in their outer shell. These elements gain electrons
to form negative ions (anions). The resulting simple ions also obey the octet rule and have an electron
arrangement like the noble gas at the end of the period. For example:
P + 3e− → P3−
S + 2e− → S2−
Cl + e− → Cl−
P3−, S2− and Cl− all have the same electronic structure as Ar and hence are isoelectronic.
The atoms of noble gases in group 18 have a stable electron arrangement with filled outer shells. Only krypton,
xenon and radon form compounds and, even then, only with the most electronegative atoms: fluorine and
oxygen.
Most transition metal atoms are capable of forming ions with different charges but many cannot lose enough
electrons to attain a noble gas electron configuration.
How does the trend in successive ionization energies of transition

elements explain their variable oxidation states?
Transition metals exhibit variable oxidation states of differing stability. Many of these atoms have, and
easily lose, 4s electrons so an oxidation state of +2 is common. However, because the 3d sublevels have
energy levels very close to that of the 4s sublevel, it is relatively easy for the 3d electrons to also be lost
leading to the formation of other oxidation states.
Ions with different oxidation states have different stabilities and the conversion from one oxidation state to
another – an important aspect of transition metal chemistry – is often characterized by a distinct colour
change.
The sum of the ionization energies is one factor in determining the relative stability of transition metal
oxidation states. Figure S2.A3 compares the successive ionization energies of calcium (1s2 2s2 2p6 3s2 3p6
4s2) from group 2 with those of titanium (1s2 2s2 2p6 3s2 3p6 3d2 4s2), a transition metal. For calcium, the
increase between the second and third ionization energies is significantly greater than that between the first
and second (or third and fourth). Formation of a Ca3+ ion is unlikely because of the relatively large increase
in energy required to remove the third electron from a 3p orbital much closer to the nucleus.
Figure S2.A3 The first six successive ionization

energies of calcium and titanium
However, for titanium, the increase in successive energy is more gradual because the 3d and 4s sublevels are
close in energy. Hence oxidation states of +2, +3 and +4 exist, but not +5 since that would mean removing a
core electron from a 3p sublevel.
How is formal charge used to predict the preferred structure of sulfate?

In chemistry, formal charge is the charge assigned to an atom in a molecule assuming that electrons in all
chemical bonds are shared equally between atoms, regardless of relative electronegativity.
The best Lewis formula for a molecule (or the major resonance structure) is that in which the formal charge
on each of the atoms is as close to zero as possible. The formal charge, FC, is given by the equation:
𝐵𝐵
FC = V – N –
2
where V is the number of valence electrons in the isolated atom, N is the number of non-bonding valence
electrons on the atom when in the molecule, and B is the total number of electrons shared in bonds with other
atoms in the molecule.
So, in carbon dioxide O=C=O
• formal charge of the carbon atom = 4 – 0 – (8/2) = 0
• formal charge of each oxygen atom = 6 – 4 – (4/2) = 0
If the formal charges on the individual atoms are low, this means less charge has been transferred. In general,
the structures in which the least charge has been transferred are the most stable as they represent the lowest
energy arrangements.
To illustrate this, consider the structures for the sulfate(VI) ion suggested in Figure S2.A4. Structure (a)
obeys the octet rule but, because sulfur is in period 3, it can expand its octet and have more than four pairs of
electrons in its valence shell. This leads to the alternative possible structures shown in (b) and (c).
Calculating the formal charges on the atoms in each suggested structure shows that version (c), in which
Figure S2.A4 Possible structures and formal charges for the sulfate(VI) ion (arrows represent coordination bonds)
there are 12 electrons around the central sulfur atom, involves the least charge transfer to the sulfur atom. It
is, therefore, the preferred structure of the sulfate(VI) ion.
The FC calculation for the preferred Lewis formula on the far right of Figure S2.A4 is as follows:
• top and bottom oxygens: FC = 6 – [1/2 × 2 + 6] = 1

• left and right oxygens: FC = 6 – [1/2 × 2 + 4] = 0
• central sulfur = 6 – [1/2 × 12 + 0] = 0
What experimental data demonstrate the physical properties of ionic

compounds?
Inquiry processes Inquiry process 2 Collecting data
There are a number of observations that provide empirical evidence that a compound is either ionic or has
significant ionic character. These are summarized in Table S2.A1.
Table S2.A1 Evidence for significant ionic character
Evidence Comments
Substances exist as a solid under standard This property is shared by some covalent substances such as
conditions with high melting and boiling diamond, silicon dioxide, silicon carbide and organic
points polymers
Does not conduct electricity in the solid, but Strong electrostatic forces prevent ionic movement in the
conducts if molten or in aqueous solution solid, but in the liquid phase ions can move freely and carry
charge
X-ray diffraction studies show little sharing The electron diagram may not give a complete description
of electron density
Lattice enthalpy can be accurately calculated This prediction may not match with predictions made from
by assuming that spherical ions are present other experimental evidence
All common ionic compounds are non-volatile solids at room temperature and pressure. They generally do
not undergo sublimation or significant evaporation when heated.
Ionic compounds do not conduct electricity in the solid state but become conducting if molten. Often the ions
in an ionic solid can move sufficiently well within the crystal lattice to allow some conduction to occur just
below the melting point. The inference from this observation is that the heating disrupts the lattice which
then releases mobile ions. However, another possible inference from this observation is that ions are formed
from the atoms during the melting process. The ions could be the product of a reaction, rather than being
present in the solid before the reaction.
If an ionic compound is soluble it will dissolve in water to form a conducting solution. Again, the inference
is that conductivity is due to the presence of ions that are present in the solid.
Water is a good solvent for ionic crystals
because it consists of polar molecules with a
positive end that can attract negative ions and a
negative end that can attract positive ions.
Many ionic compounds are, therefore, soluble
in water and the mixing that occurs during
dissolving is accompanied by an increase in
entropy. Insoluble ionic compounds usually
have small and highly charged ions and high
lattice energies. The observation that some
ionic compounds are insoluble in water can be
explained by inferring that the ionic bonding
within the lattice is stronger than the ion–
dipole forces formed when the ionic solid
dissolves and hydrates. The increase in entropy
is insufficient to make the process favourable.
Evidence that ionic solids contain ions is
derived from calculations involving lattice
energies and X-ray diffraction. Figure S2.A5
shows that the electrons are distributed around
Figure S2.A5 Electron density map of sodium chloride
each nucleus in a similar way and that there are obtained from X-ray diffraction analysis of crystals
regions between the ions where the electron
density is negligible. This is in agreement with
their physical properties.
However, X-ray diffraction studies have shown

that the ionic model is not so accurate for
lithium fluoride, LiF. Figure S2.A6 shows that
the lithium ion is not perfectly spherical and
that there are regions between the lithium and
fluoride ions where the electron density is
measurable. This is related to lithium fluoride
having some covalent character. This is the
result of the polarizing ability of the small
lithium cation and leads to a low solubility in
water and a solubility in non-polar solvents
that is high compared to that of sodium
chloride, NaCl.
Figure S2.A6 Electron density map of lithium

fluoride obtained from X-ray diffraction analysis
How can lattice enthalpies and the bonding continuum explain the trend
in melting points of metal chlorides across period 3?
The chlorides of the electropositive metals tend to be ionic and can be made by the direct synthesis of the
elements as well as by reacting the metal with hydrochloric acid in reactions such as:
2Na (s) + Cl2 (g) → 2NaCl(s)
Mg (s) + 2HCl (aq) → MgCl2 (aq) + H2 (g)
Table S2.A2 summarizes the melting points and lattice energies of the metal chlorides in period 3.
Table S2.A2 Properties of sodium, magnesium and aluminium chlorides
Compound Formula Lattice enthalpy Electronegativity difference Melting Reaction

/ kJ mol−1 between metal and chlorine point / °C with water
sodium NaCl 790 2.3 (>1.7) 801 none
chloride [Na+ Cl−]
magnesium MgCl2 2540 1.9 (>1.7) 712 slight
chloride [Mg2+ 2Cl−] hydrolysis
aluminium AlCl3 none 1.6 (<1.7) 192 * rapid
chloride (at 2 atm) hydrolysis
* Solid aluminium chloride, AlCl3 (s), sublimes and exists as a dimer with the molecular formula Al2Cl6 in
the vapour state.
Going from left to right across a period, the electronegativities of the elements increase and so the chlorides
gradually become less ionic and more covalent.
Despite being the chloride of a metal, anhydrous aluminium chloride (AlCl3(s)) does not have ionic bonding:
the difference in electronegativity is less than 1.7 which suggests the bonding is covalent. This prediction,
based on a ‘rule of thumb’, is borne out by the properties of anhydrous aluminium chloride. The bonding in
aluminium chloride is best described as polar covalent bonding.
It should be noted that the lattice enthalpy refers to the dissociation of an ionic solid to form widely
separated gaseous ions with negligible interactions. This process is very different from melting, which is the
conversion of a solid to a liquid at constant temperature. In an ionic liquid the ions are close to each other
and there will still be considerable ionic bonding.
Because the two processes of lattice dissociation and melting are very different, we would not expect a direct
relationship between lattice enthalpy and melting point. However, the electrostatic forces of attraction
between oppositely charged ions are often large and so ionic solids tend to have high melting points.
The behaviour of the metal chlorides with water is also related to the type of bonding.
The ionic chlorides of the Group 1 elements dissolve in, but do not react with water and can be recovered
unchanged by the evaporation of the water.
Aluminium chloride hydrolyses in water to form hydrochloric acid:
AlCl3 (s) + 3H2O (l) → Al(OH)3 (s) + 3HCl (aq).
Aluminium compounds are more acidic than magnesium compounds because the small and highly charged
Al3+ (aq) ion has a significantly higher charge density than the larger Mg2+ ion.
Most covalent chlorides are rapidly hydrolysed in water and release colourless fumes of hydrogen chloride
gas which dissolves to give an acidic solution of hydrochloric acid:
PCl5 (s) + 4H2O (l) → H3PO4 (aq) + 5HCl (aq)
S2.2 The covalent model
Why do ionic bonds only form between different elements while

covalent bonds can form between atoms of the same element?
Themes S2.1 The ionic model
It is important to understand that ionic and covalent bonding are not discrete categories, and that it is
possible for some compounds, (for example, AlCl3) to possess both ionic and covalent character in its
bonding.
How atoms interact with each other to form bonds in compounds depends (in part) on the relative values of
the atom’s electronegativity: the ability of an atom in a molecule to attract a shared pair of electrons to itself.
Electronegativity values are, therefore, useful in predicting whether a bond is non-polar covalent, polar
covalent or ionic. A large electronegativity difference between two atoms results in ionic bonding. This
typically occurs between atoms of metals and non-metals; for example, in NaCl and K2O. Ionic bonding
requires one atom to gain an electron (e.g. Cl and O) and the other one to lose an electron (e.g. Na or K) and
hence requires a difference in electronegativity. In an element (e.g. H2) all atoms are the same and so have
the same electronegativity.
A small electronegativity difference results in a polar covalent bond.
This typically occurs between atoms of non-metals; for example, in
H2O or HCl. If the atoms have the same electronegativity (as in, for
example, H2) they will form non-polar covalent bonds.
A simple ‘rule of thumb’ is that if the electronegativity difference is
greater than about 1.7, the bond is likely to be dominantly ionic. If
the electronegativity difference is zero, the bond will be non-polar
covalent. If the electronegativity difference is between these two Figure S2.A7 Electron density for
values, the bond will probably be polar covalent to a greater or lesser the hydrogen molecule, H2
extent.
In a non-polar covalent bond, the electron density between the two atoms will be symmetrical (Figure
S2.A7). The electron density can be deduced from molecular orbital theory which combines pairs of atomic
orbitals to form new molecular orbitals.
In a polar covalent bond, electron pairs are not equally shared between the two atoms and the electron
density between the two nuclei is greater around the atom with the greater electronegativity. A dipole is
formed with a partial negative charge on the more electronegative atom. The less electronegative atom has
an equal but opposite sized positive charge and is slightly electron deficient.
Figure S2.A8 The spectrum of bonding from covalent to ionic
There is a continuous change from non-polar covalency to polar covalency to strongly ionic bonding.
Substances which have polarized ionic bonding, such as silver(I) iodide, AgI, contain ions in a lattice but the
electron cloud of the iodide anion is distorted by the silver(I) ion with some electron density between the two
ions which means that the bonding is not purely ionic, but possesses some covalent character. For example,
silver(I) iodide is less soluble in water and more soluble in ethanol compared to silver(I) chloride. The
covalent character of silver(I) iodide results in a lower melting point and hence lower thermal stability
compared to silver(I) chloride.
In strongly ionic bonding, there is little sharing of electron pairs but a nearly complete transfer of electrons
from the less electronegative atom to the more electronegative atom.
What are some of the limitations of the octet rule?

Nature of Science Theories
Electron-deficient compounds
In gaseous beryllium chloride, BeCl2 (g), the
beryllium atom in each molecule has only four
electrons in its valence shell and is electron
deficient. The boron trichloride molecule, BCl3, is
also electron deficient: the central boron atom has
only six electrons in its valence shell (Figure
S2.A9). A related example of an electron-deficient
molecule is the gaseous aluminium trichloride, Figure S2.A9 Lewis formulas for BeCl2 (g) and BCl3 (g)
molecule, AlCl3 (g).
Molecules with an expanded octet
Molecules with an expanded octet have a central
atom which has more than eight electrons in its
valence shell (Figure S2.A10). Examples are
phosphorus pentafluoride, PF5, and sulfur
hexafluoride, SF6. In phosphorus pentafluoride,
there are five single covalent bonds (10 electrons
around the phosphorus atom) and in sulfur
hexafluoride, SF6, there are six single covalent Figure S2.A10 Lewis formulas for sulfur hexafluoride,
bonds (12 electrons around the sulfur atom). SF6, phosphorus pentafluoride, PF5,and PCl6−
Odd-electron molecules
In most stable molecules, the number of electrons is
even and complete pairing of electrons occurs.
However, a small number of molecules and ions
contain an odd number of valence electrons. Most
odd-electron molecules have a central atom from an
odd-numbered group, such as nitrogen or chlorine.
Nitrogen monoxide, NO, and nitrogen dioxide,
NO2, (Figure S2.A11) are examples of odd-electron Figure S2.A11 Lewis formulas for nitrogen monoxide and
molecules. Both exist as resonance hybrids of two nitrogen dioxide
Lewis formulas.
Molecules and ions with an unpaired electron can be detected spectroscopically and are known as radicals.
Radicals are very reactive: the oxy-chlorine radical, OCl, is an intermediate formed during the destruction
of ozone by chlorofluorocarbons (CFCs).
Why do noble gases form covalent bonds less readily than other
elements?
The group 18 elements exist as monatomic gases. Historically, these noble gases were known as ‘inert’ gases
due to their seeming lack of reactivity. Atoms of all these elements have a closed-shell configuration in
which the valence shell is complete – containing two electrons in the case of helium and eight in atoms of the
other noble gases. In accordance with Hund’s rule and the Pauli exclusion principle, all electrons in a noble
gas atom are paired.
Much chemical reactivity can be accounted for by the tendency of elements with open-shell configurations
(partially filled valence shells) to achieve stable and relatively unreactive closed-shell configurations. This is
often summed up in the octet rule, the notion that species with eight valence electrons are stable and hence
unreactive. (In the case of helium, this is modified to the duplet, or duet, rule.)
It is, however, incorrect to assume that all noble gas electron configurations are equally stable and hence
unreactive. As early as 1902, Professor Giuseppe Oddo suggested in a letter to Sir William Ramsay (the
chemist who first isolated helium and argon and discovered neon, krypton and xenon) that krypton and
xenon ought to show a tendency to form chemical compounds.
We would expect the heavier noble gas atoms to be more reactive because their valence electrons have lower
ionization energies and because the electron clouds surrounding their nuclei are larger and more diffuse,
making them more polarizable.
Polarizability is a measure of how readily
an electron cloud can be distorted by
interaction with an electric field. Small,
highly electronegative atoms, such as
fluorine and oxygen, have highly charged
and relatively unshielded nuclei. This
makes them highly polarizing: they can
easily distort the large, diffuse electron
cloud around a noble gas atom leading to
orbital overlap and hence bond formation.
It was not until the 1960s that the first
noble gas compounds were discovered.
These were mostly fluorides, oxides or
oxyfluorides of krypton and xenon
including XeF4, XeF2, KrF2, XeOF4 and
XeO4 (Figure S2.A12). Krypton and xenon
remain the only group 18 elements for
which compounds have been prepared in
macroscopic amounts. In the compounds Figure S2.A12 Compounds of xenon
that have been synthesized and structurally
characterized, the gases have the following
oxidation states: krypton; +2 and xenon; +2, +4, +6, and +8.
A complete understanding of how these compounds form depends on detailed molecular orbital theory.
Why do Lewis acid-base reactions lead to the formation of coordination

bonds?
Lewis theory defines acids and bases in terms
of electron pair donation and acceptance. A
Lewis base is an electron pair donor, and a
Lewis acid is an electron pair acceptor. Figure
S2.A13 shows the reaction between boron
trifluoride and trimethylamine to form a Lewis
adduct. Figure S2.A13 Lewis acid-base reaction
A coordination bond is formed as a result of
the donation of an electron pair from the donor.
The donor of the electron pair may be a molecule
or an anion and, if a complex ion is formed, it is
described as a ligand. The acceptor orbital may
be a p orbital, as in boron trifluoride, or an empty
s orbital in, for example, H+, or a d orbital in a
transition metal ion or atom in a complex ion.
Figure S2.A14 Sulfur dioxide acting as a Lewis acid and
A molecule like sulfur dioxide, SO2, that has the oxide ion acting as a Lewis base
both an available lone pair and an empty orbital,
may function as a Lewis base and a Lewis acid (for example, with oxide ions) (Figure S2.A14).
How does the presence of double and triple bonds in molecules

influence their reactivity?
Bond strength, as measured by bond enthalpy, is one factor that influences the reactivity of a molecule.
Molecules with high bond enthalpy will result in a reaction having a high activation energy and hence a slow
rate of reaction.
Nitrogen, N≡N, is relatively unreactive because it has a fairly strong
triple bond: the energy required to form atoms from the molecule is
945 kJ mol–1. Oxygen is much more reactive than nitrogen: it only
takes 498 kJ to break a mole of O=O bonds.
However, it is important to compare bonds of the same type if
reactivity is being compared. For example, C=C bonds tend to be
more reactive than C–C bonds, because when C=C bonds react, only
the weaker of the two bonds in the double bond usually breaks,
leaving the stronger single bond intact.
The polarity of a bond and whether a bond is a σ bond (sigma bond)
or a π bond (pi bond) also plays a large part in determining chemical Figure S2.A15 The structure and
reactivity. A double bond is composed of one strong sigma bond and electron density of a carbon-
a weaker pi bond (Figure S2.A15). When molecules with pi bonds carbon double bond
react, the reaction is usually initiated by the breaking of the weaker
and more polarisable pi bond.
The electrons in the pi bond are further from the two nuclei and are more loosely held than the sigma
electrons. A strong electrophile (electron pair acceptor) has an affinity for these loosely held electrons. It can
pull them away to form a new bond.
The bond enthalpy of the pi bond in a double bond can be easily calculated by determining the difference
between the bond enthalpies of a carbon–carbon double bond and a carbon–carbon single bond:
614 kJ mol−1 − 346 kJ mol−1 = 268 kJ mol−1
The pi bond therefore has approximately 75% of the strength of the sigma bond in ethene and ethane.
Many of the reactions of alkynes are similar to the corresponding reactions of alkenes because both involve
pi bonds between two carbon atoms. Like the pi bond of an alkene, the pi bonds of an alkyne are electron-
rich, and they readily undergo addition reactions. Bond enthalpies can again be used to calculate the average
bond enthalpy of each of the two pi bonds in ethyne:
(839 kJ mol−1 – 346 kJ mol−1) ÷ 2 = 246.5 k J mol−1.
Despite having weaker pi bonds, an alkyne is less reactive than an alkene in terms of electrophilic addition
reactions. This observation can only be explained by considering the thermodynamic stabilities of the
reactants and the transition states for alkenes and alkynes.
How does the ability of some atoms to expand their octet relate to their
position in the periodic table?
Nitrogen (in period 2) forms one chloride, nitrogen trichloride, NCl3. Phosphorus (in period 3), forms two
chlorides: phosphorus trichloride, PCl3, and phosphorus pentachloride, PCl5. Phosphorus can form five
bonds since it has low-energy 3d orbitals to accommodate the extra electrons, while nitrogen has no such
orbitals available in the second shell, n = 2.
The energy required to promote a 3s electron in the phosphorus atom (Figure S2.A16) to the empty 3d
orbital to form five unpaired electrons is more than compensated for by the even larger amount of energy
released when two extra P–Cl bonds are formed in PCl5.
Figure S2.A16 Expansion of the octet in phosphorus to form PCl5
Only atoms from periods 3 and above can form molecules with expanded octets because their formation
depends on the presence of empty low-energy d orbitals and a relatively large atom centre. Thus, PCl5 exists
but not PI5: it is not possible to pack five large iodine atoms around a central phosphorus atom without
significant repulsion. Since size is a factor, molecules with expanded octets are most stable when the central
atom is bonded to small and electronegative atoms such as fluorine, chlorine and oxygen and they also form
high energy bonds to compensate for the electron promotion energy. Metal atoms and cations can also be
identified by their octet and form complexes, e.g. [PbCl6]2−.
Sulfur hexafluoride (Figure S2.A17), SF6, is another example of a stable molecule with an expanded octet: in
this compound, each sulfur atom is surrounded by twelve valence electrons. The central sulfur atom can
form six single bonds by promoting electrons from the 3s and 3p sublevels to form six unpaired electrons.
Figure S2.A17 Expansion of the octet in sulfur to form SF6
How useful is the VSEPR model at predicting molecular geometry?

The VSEPR model was developed in detail by Ronald Gillespie and Ronald Nyholm in the late 1950s and is
used for predicting the shapes (geometries) of molecules based on the arrangement of electron pairs around a
central atom.
A central atom is defined as an atom which is bonded to two or more other atoms, while a terminal atom is
bonded to only one other atom. The number of electron pairs (domains) around the central atom (whether
bonding or non-bonding) is determined by first drawing a Lewis formula. Multiple bonds (double or triple)
are counted as a single electron domain. The number of atoms bonded to the central atom is called the
coordination number. When the number of lone pairs is added to the coordination number the steric number
is obtained.
The electron domains repel each other and sit as far away from each other as possible (to minimize the
energy) with the repulsions varying in strength in the following order: lp–lp > lp–bp > bp–bp where lp and
bp stand for lone pair and bonding pair respectively.
For example, in ammonia (NH3) the coordination number of the central nitrogen atom is 3; when the lone
pair on nitrogen is added the resulting steric number is 3 + 1 = 4. The four electron domains repel each other
giving rise to an approximately tetrahedral arrangement of electron domains, and a consequent trigonal
pyramidal geometry for the ammonia molecule. Because the lone pair is unshared and held closer to the
central nitrogen atom, it repels the N–H bonding pairs more strongly than the bonding pairs repel each other
and leads to H–N–H bond angles that are smaller than the tetrahedral bond angle (~107°).
Models are used to explain and make predictions about aspects of reality. The assumptions made in creating
a model cause there to be differences between the model and reality and can lead to exceptions not predicted
by the model. There are some groups of compounds where the VSEPR model fails to predict the correct
geometry.
The VSEPR model neglects the fact that the size of the atom or group (ligand) bonded to the central atom
influences the amount of repulsion between adjacent domains (ligand–ligand repulsion). The size of the
electron cloud influences the amount of repulsion experienced by an adjacent atom or group of atoms.
The Cl2O molecule (Figure S2.A18) has a Cl–O–Cl bond angle of
111.2°, larger than both the 104.5° of water and the tetrahedral bond
angle of 109.5°. This discrepancy cannot be explained by the VSEPR
model alone. The large size of the chlorine atoms prevents them from
being pushed any closer by the lone pairs on oxygen. Figure S2.A18 Structure and
shape of dichlorine oxide, Cl2O
The molecule tris(trimethylsilyl)amine, (CH3Si)3N, (Figure S2.A19), has
Si–N–Si angles of 120° despite the lone pair on the nitrogen. The
VSEPR model would predict an angle close to 109.5° for this molecule,
but the large ligands repel each other significantly and the nitrogen lone
pair is not well localized.
VSEPR theory works well for main group compounds but is less useful
for transition metal compounds because lone pairs in transition metal
complexes do not occupy directional orbitals. The shape of a complex
ion can usually be deduced by counting the ligands and placing them as
far apart from each other around the central metal ion as possible.
VSEPR theory also fails for very strongly ionic systems such as the Figure S2.A19 Structure of
molecule Li2O (g), which is formed when solid lithium oxide is tris(trimethylsilyl)amine
vaporized. Li2O (g) is linear with repulsion of positively charged
lithium atoms being the dominant factor. It is more correctly regarded as 2Li+ O2- because the oxide ion is
not very polarisable. If lithium oxide (Li–O–Li) were covalent, VSEPR theory would predict a bent or V
shape like that of H2O since the oxygen atom is surrounded by two bonding and two non-bonding pairs of
electrons.
What properties of ionic compounds might be expected in compounds

with polar covalent bonding?
Table S2.A3 Relation between
This question links material from: electronegativity difference (Δχ)
and character of single bonds
Δχ Amount of ionic
Ionic and covalent bonding are not sharply distinct categories: bonding
(χA − χB) character / %
exists on a continuum from non-polar covalent (in homonuclear
0.2 1
diatomic molecules such as H2 and I2) when there is no electronegativity
difference between the bonded atoms; through polar covalent; to nearly 0.4 4
pure ionic bonding when there is a large difference in electronegativity 0.6 9
between the bonded metal and non-metal (Table S2.A3). 0.8 15
1.0 22
For this reason, it is common to introduce the concept of the percentage 1.2 30
of ionic or covalent character in a particular bond. Nobel laureate Linus 1.4 39
Pauling proposed an equation (derived from empirical data) for 1.6 47
estimating the percentage of ionic character in a bond between two 1.8 55
elements:
2.0 63
2
amount of ionic character = [1 − 𝑒𝑒 −0.25(𝜒𝜒𝐴𝐴 −𝜒𝜒𝐵𝐵 ) ] × 100 2.2 70
2.4 76
where χA and χB are the respective electronegativities of the bonded 2.6 82
atoms A and B. 2.8 86
3.0 89
3.2 92
Another way to semi-quantitatively predict whether a chemical bond will possess appreciable covalent or
ionic character is via the application of Fajans’ rules, developed by Kazimierz Fajans in 1923. According to
Fajans’ rules (Table S2.A4), the extent to which a cation and anion will bond covalently depends on the
charge on the cation and the relative sizes of the cation and anion.
Table S2.A4 Fajans’ rules
Covalent Ionic
small cation (< ~100 pm) large cation (> ~100 pm)
large anion small anion
high charges low charges
The ability of a cation to distort the electron cloud around an anion is its polarization power, and the
tendency of the electron cloud around an anion to be deformed by a cation is referred to as its polarizability
or softness. Polarizing power increases with
increasing charge and decreasing cation size or, in
other words, increasing charge density. The larger the
electron cloud around an anion, the more polarizable
(softer) it will be. The greater the extent to which the
electron clouds of the cation and anion overlap, the
greater the covalent character of the bond.
The conductivity of molten beryllium chloride is only
a thousandth that of sodium chloride under similar
conditions, showing that the beryllium salt has less
ionic character than the sodium salt. Li+ and Be2+ are
small cations with high charge densities and their
compounds possess greater covalent character than Figure S1.A20 Increasing cation charge and increasing
those of the larger cations in their respective groups. anion polarizability give rise to increasing covalent
character
What features of a molecule make

it “infrared (IR) active”?
The ability of some molecules to absorb and re-
emit infrared radiation is what makes certain
molecules, including CO2, H2O and CH4, ‘IR
active’. When a molecule absorbs infrared
radiation, the shape will alter due to changes such
as the stretching or bending of bonds (Figure
S2.A21), or internal rotation around single bonds.
The covalent bonds behave like springs and obey
Hooke’s law. Bond stretching requires more Figure S2.A21 Bond stretching and bond bending (also
energy than bond bending and therefore bond- known as wagging or rocking)
stretching requires absorption of shorter
wavelength (higher frequency) radiation than bond-bending.
For a molecule to be IR active, it must possess a specific feature: a bond dipole moment which changes
during the vibration.
Diatomic molecules of elements such as hydrogen, oxygen and the

halogens (Figure S2.A22), do not experience a change in dipole
moment during a vibration and therefore will not absorb in the
infrared region of the electromagnetic spectrum.
Molecules such as the hydrogen halides (Figure S2.A23) that are
Figure S2.A22 Bond stretching in
composed of two different atoms have a permanent dipole because of
the non-polar chlorine molecule
the difference in electronegativity of their component atoms.
Stretching or bending alters the distance between the centres of
positive and negative charge and so changes the dipole moment. Figure S2.A23 Bond stretching in
the hydrogen chloride molecule
Carbon dioxide is a linear molecule and has three possible vibration
modes (Figure S2.A24).
Figure S2.A24 Stretching and bending (rocking) vibrations in the carbon dioxide molecule
In symmetric stretching, both carbon–oxygen bonds lengthen at the same time. The dipole moments of each
bond increase, but they act in opposite directions and so cancel out. There is no change in the overall dipole
moment of the carbon dioxide molecule and so symmetric stretching is IR inactive. The other two modes,
however, do result in dipole changes and are IR active.
A water molecule (Figure S2.A25) has modes of vibration similar to those of the carbon dioxide molecule.
However, in this case, all the vibration modes are IR active. In a ‘bent’ molecule the changes in bond dipole
for symmetric stretching are not in opposite directions. They do not cancel out vectorially and, because there
is a change in the overall dipole moment of the molecule, infrared absorption occurs.
Figure S2.A25 Stretching and bending vibrations in the water molecule
What are the different assumptions made in the calculation of formal

charge and of oxidation states for atoms in a species?
R3.2 Electron transfer reactions
Chemists have developed a very simple ‘bookkeeping method’ to determine if an atom within a molecule or
ion is neutral or has a positive or negative charge. These assigned integer charges are called formal charges.
A formal charge is a comparison of electrons ‘owned’ by an atom in a Lewis formula versus the number of
electrons possessed by the same atom in its unbound, free atomic, state. Formal charge is, therefore, a
chemical method for estimating the distribution of electric charge within a molecule.
Knowledge of charge distribution (identification of atoms that are electron-rich or electron-poor) is useful in
organic chemistry. This is because charge distribution can help explain mechanisms: how and why reactions
occur. The formal charge concept is also used to identify the most likely Lewis formula for a molecule or
ion.
In the formal charge model, the electrons in each
covalent bond are assumed to be split exactly
evenly between the two atoms in the bond; the
bonds are considered purely covalent, in contrast to
the oxidation state model which treats bonds as
ionic and ‘gives’ the electrons in the bonds to the
atom with the greater electronegativity. These two
models should be seen as opposite ends of a
continuum with the real charge on atoms being in
between the two extremes. Figure S2.A26 shows
the formal charges and oxidation states of the atoms
in a carbon dioxide molecule.
These are fundamentally different ways of
representing the distribution of electrons amongst Figure S2.A26 Formal charges and oxidation
the atoms in the molecule. states in the CO2 molecule
The covalent (electron pair sharing) nature of the
bonding is overemphasized in the use of formal charges: in this example, in reality there is a higher electron
density around the two oxygen atoms as they have higher electronegativity than the carbon atom.
The model of oxidation states overemphasizes the ionic nature of the bonding: in this case, the difference in
electronegativity between carbon and oxygen is not sufficient to regard the bonds as being ionic in nature.
Why are silicon-silicon bonds generally weaker than carbon-carbon

bonds?
Silicon–silicon bonds are much weaker than carbon–carbon bonds:
the Si–Si bond enthalpy is 158 kJ mol−1 compared to 346 kJ mol−1 for
C–C. These values are a measure of the sigma bond strength and
explain, in part, why compounds with carbon–carbon single bonds
are less reactive and more stable than the corresponding compounds
with silicon–silicon single bonds and why we do not get molecules
containing long chains of silicon atoms. A silicon atom has almost
twice the diameter of a carbon atom (114 pm compared to 75 pm), so
silicon has a lower electron density and less effective orbital overlap
during bond formation. The shared pairs of electrons are further
away from the two larger silicon atoms than from the two smaller
carbon atoms, forming longer and weaker single bonds (Figure
S2.A27).
Silicon exists as a diamond-like covalent network structure with Figure S2.A27 pi-bond formation
single bonds only; it does not form allotropes that are structurally in carbon and silicon
similar to graphite or C60, because the weakness of the Si–Si pi bonds
means silicon is unable to form stable double and triple bonds like carbon. Phosphorus and sulfur, like
silicon, do not form strong π bonds between atoms of the same element because the p orbitals are larger and
the electron density is more diffuse (spread out), hence the overlap is poor. This explains why there are no
stable P2 molecules (with a triple bond) and no stable S2 molecules (with a double bond). However, sulfur
and phosphorus can form π bonds with oxygen. These double bonds are greatly strengthened by their polar
character.
Catenation is the ability of a non-metallic element to form covalent bonds with atoms of itself to give long
chains or rings (cyclic compounds). This is especially important in carbon as carbon–carbon bonds are the
basis for organic chemistry. Catenation becomes less extensive as group 14 is descended, partly due to the
longer and weaker covalent bonds.
Silicon has p orbitals significantly larger than those of oxygen. Their differences in size and energy mean
that extensive overlap does not occur (Figure S2.A28).
Figure S2.A28 Effective and ineffective overlap of p orbitals to form C=O and hypothetical Si=O bonds
Consequently silicon dioxide, SiO2, has a giant covalent structure where the bonds are –O–Si–O– bonds. No
stable SiO2 (O=Si=O) molecules are possible in the solid state.
The formation of strong π bonds only occurs in molecules formed by the elements carbon, nitrogen and
oxygen from period 2 of the periodic table. Examples include CO2, CO, N2, O2, HCN and NO2.
How do the terms “bonds” and “forces” compare?

Nature of Science Models
The principal forces acting within and between atoms and molecules are electrostatic in nature. These forces
may be attractive (between opposite charges: for example, protons and electrons or cations and anions) or
repulsive (between like charges). The magnitude of an electrostatic force can be calculated using Coulomb’s
Law:
𝑘𝑘|𝑞𝑞1 𝑞𝑞2 |
|𝐹𝐹| =
𝑟𝑟 2
where F is the force between the two charged particles (in newtons), q1 and q2 are the charges on the
respective particles (in coulombs) and r is the distance between them (in metres). k is a proportionality
constant (Coulomb’s constant, k ~ 8.988 × 109 N m2 C−2).
When referring to intermolecular interactions we refer, for example, to hydrogen bonds. The force involved
in a hydrogen bond is a particularly strong dipole–dipole interaction between a δ+ hydrogen atom and the
lone pair on a δ− oxygen atom. This force is, ultimately, electrostatic in nature.
A chemical bond arises from the resolution (or balancing) of the repulsive and attractive electrostatic forces
between two atoms (Figure S2.A29), leading to a more stable state of lower chemical potential energy. For
this reason, the formation of a chemical bond is exothermic and heat energy is released to the surroundings.
Figure S2.A29 A representation of the chemical bond between two

hydrogen atoms, showing the interactions between electrons and nuclei
As two atoms approach each other their chemical potential energy decreases to a minimum at their
equilibrium separation distance, which represents a minimum of chemical potential energy (Figure S2.A30).
If the atoms come any closer together the repulsion between the nuclei begins to dominate and the chemical
potential energy of the system rises exponentially as the internuclear distance decreases. Note that when the
two atoms are separated by an infinite distance, their chemical potential energy is, by definition, zero.
Figure S2.A30 How the chemical potential energy of two hydrogen atoms varies with separation
A stable covalent bond has formed when the atoms reach the distance corresponding to the minimum energy.
Bringing the atoms any closer together results in a rapid increase in energy. The distance between the two
bonded nuclei is known as the bond length. The energy per mole required to separate the atoms in the bond
is known as the bond dissociation enthalpy.
When referring to intermolecular interactions we refer, for example, to hydrogen bonds. The force involved
in a hydrogen bond is a particularly strong dipole-dipole interaction between a δ+ hydrogen atom and the lone
pair on a δ− oxygen atom, which is ultimately electrostatic in nature.
All chemical bonds (‘bonds’) and intermolecular forces (‘forces’) are ultimately electrostatic in nature with
chemical bonds (ionic, covalent and metallic bonding) generally being stronger than intermolecular forces
which also includes hydrogen bonds.
What experimental data demonstrate the physical properties of covalent

compounds?
Tools Tool 1 Experimental techniques
Inquiry processes Inquiry process 3 Concluding and evaluating
Melting and boiling points along with conductivity data demonstrate the physical properties of covalent
compounds.
There are two distinct classes of covalent compounds, covalent network and simple molecular, which have
very different physical properties. A molecular substance contains discrete molecules with weak
intermolecular forces operating between molecules in the solid and liquid states. A network covalent
substance has only strong covalent bonds between atoms.
In general, network solids have very high melting and boiling points, are electrical insulators and hard.
Examples of network solids with these properties include diamond, silicon and silicon dioxide.
Molecular solids are much softer and have much lower melting points and boiling points than network
solids.
Graphite is a network solid but soft (due to its layered structure) and an electrical conductor (due to the
presence of delocalized electrons). It does not have all the typical properties of network covalent substances.
Table S2.A5 summarizes the physical properties of network and molecular covalent substances.
Table S2.A5 Physical properties of covalent substances
Covalent substance Melting point Boiling point Electrical conductivity

network covalent very high very high poor (unless graphite)
molecular covalent low low Poor
To what extent does a functional group determine the nature of the

intermolecular forces?
The physical properties of molecular compounds, including organic compounds, are determined to a large
extent by the type of intermolecular force(s).
Consider two compounds with similar molecular masses: ethane, C2H6, (Mr = 30) and methanol, CH3OH
(Mr = 32). The most significant structural difference between them is that ethane has had one of its methyl
groups substituted by a hydroxyl functional group, –OH. This must, therefore, play a large role in their very
different chemical and physical properties. Ethane (boiling point − 89 °C) is a non-polar molecule and
essentially insoluble in water. Methanol (boiling point 65 °C) is a polar molecule and miscible and soluble in
water in all proportions.
Alkanes are non-polar molecules (due to their symmetrical arrangements of C–H bonds) and are thus held
together in the solid and liquid states only by relatively weak London (dispersion) forces. The boiling points
of alkanes with one to four carbon atoms are so low that all of these molecules are gases at room
temperature. By contrast, compounds that contain a hydroxyl functional group – even methanol, with only
one carbon atom – are liquid at room temperature. The boiling points of alcohols are significantly higher
than hydrocarbons of similar molecular mass (Table S2.A6) because they can form hydrogen bonds which
are the strongest of the intermolecular forces.
Table S2.A6 Comparing the boiling points of selected alcohols and alkanes
Number of Alkane Alcohol Increase in

electrons in Formula Boiling point / °C Formula Boiling point / °C boiling point / °C
the molecule
18 C2H6 −88 CH3OH 65 153
26 C3H8 −42 C2H5OH 78 120
34 C4H10 0 C3H7OH 97 97
42 C5H12 36 C4H9OH 118 82
50 C6H14 69 C5H11OH 138 69
58 C7H16 98 C6H13OH 157 59
The boiling points of alcohols and alkanes both increase with molar mass (Figure S2.A31) and hence number
of carbon atoms, but the increase in boiling point is explained by the greater number of electrons available
for polarization.
In addition to forming hydrogen bonds with
other alcohol molecules, alcohols can form
hydrogen bonds with water molecules
which explains why small alcohol
molecules with one to three carbon atoms
are completely soluble. However, as the
length of the chain increases, the solubility
of alcohols in water decreases: the
molecules become more like hydrocarbons
(more non-polar) and less like water (less
polar). The alcohol 1-decanol,
CH3(CH2)8CH2OH, which contains 10
carbon atoms, is poorly soluble in water.
The amines can be derived from ammonia
by replacing one or more of the hydrogen
atoms in the ammonia molecule by alkyl
Figure S2.A31 Boiling points of alcohols and alkanes versus
groups (Figure S2.A32).
number of electrons
Figure S2.A32 Ammonia, the secondary amine dimethylamine and the primary amine phenylamine (aminobenzene)
Amines have a lone pair of electrons on the nitrogen atom, which is more readily donated than a lone pair on
the oxygen of alcohols, due to the lower electronegativity of nitrogen). This lone pair is nucleophilic towards
partially positive carbon atoms in halogenoalkanes and basic towards protons, H+.
Amines that have N–H bonds will form strong hydrogen bonds to
other amine molecules (Figure S2.A33) and water molecules. The
short-chain amines are therefore water soluble and their boiling
points are higher than those of the corresponding alkanes (see Table
S2.A7 and Figure S2.A34). The effect of hydrogen bonding on
boiling point is not as significant as it is in the alcohols.
Figure S2.A33 Intermolecular

hydrogen bonding in amines
Figure S2.A34 Boiling points of alkanes and amines
Table S2.A7 Comparing the boiling points of selected amines and alkanes
Number of Alkane Amine Increase in

electrons in Formula Boiling point / °C Formula Boiling point / °C boiling point / °C
the molecule
18 C2H6 −88 CH3NH2 −8 80
26 C3H8 −42 C2H5NH2 17 59
34 C4H10 0 C3H7NH2 49 49
42 C5H12 36 C4H9NH2 78 42
50 C6H14 69 C5H11NH2 104 35
58 C7H16 98 C6H13NH2 130 32
To what extent can intermolecular forces explain the deviation of real

gases from ideal behaviour?
Themes S1.5 Ideal gases
Real gases deviate from the ideal gas equation because real gas molecules interact with one another;
repulsive forces between molecules assist expansion and attractive forces assist compression of the gas.
Repulsive forces (which are very short-range) only become important when the gas molecules are almost
touching, which is the case at high pressures. Attractive forces operate over a longer range and become
important when molecules are quite close together, but not necessarily touching.
• At low pressure (large volume) gas molecules will be so far away from each other that, for most of
the time, intermolecular forces are insignificant and the behaviour of the gas will be close to ideal.
• At very high pressures repulsive forces will dominate and the gas can be expected to be much less
compressible.
• At intermediate pressures, when molecules are on average a few molecular diameters apart, attractive
intermolecular forces become important and the gas can be expected to be more compressible than an
ideal gas.
Deviation from ideal behaviour can be illustrated by plotting the compressibility factor (also known as the
compression factor), Z, against pressure. Under all conditions, the compressibility factor of an ideal gas
equals 1 so Z is a direct measure of departure from ideal behaviour. The compressibility factor of a real gas
is given by the formula:
𝑛𝑛𝑛𝑛𝑉𝑉m
𝑍𝑍 =
𝑅𝑅𝑅𝑅
where Vm is the molar volume of the gas.
Figure S2.A35 shows how Z varies with pressure
for nitrogen gas at a range of temperatures. The
dotted line shows that Z = 1 for an ideal gas under
all conditions. It can be seen that at very low
pressures Z tends towards 1 and nitrogen behaves
essentially ideally. At high pressures, Z >1,
indicating that nitrogen has become more difficult
to compress than an ideal gas and that repulsive
forces are dominant. Where Z < 1, attractive Figure S2.A35 Compressibility factor, Z, of N2 (g) plotted
intermolecular interactions have become against pressure (in bar) at different temperatures
important and nitrogen is easier to compress than
an ideal gas.
Figure S2.A36 shows PV curves (isotherms) for an ideal gas and a real gas. Each line represents a different
temperature and the temperature increases as the curves move towards the upper right corner.
Figure S2.A36 Pressure versus volume isotherms for an ideal gas (left) and real gas (right)
Comparison of the curves shows that, at high volumes and high temperatures, the real and ideal isotherms do
not differ significantly. The small differences suggest that the ideal gas law is correct at low pressures and is
in fact the first term in an expression of the form:
𝑃𝑃𝑃𝑃 = 𝑛𝑛𝑛𝑛𝑛𝑛(1 + 𝐵𝐵′ 𝑃𝑃 + 𝐶𝐶 ′ 𝑃𝑃2 + ⋯ )
Or alternatively,
B 𝐶𝐶
+
𝑃𝑃𝑃𝑃 = 𝑛𝑛𝑛𝑛𝑇𝑇(1 + + ⋯)
𝑉𝑉 𝑉𝑉 2
This procedure of treating a simple law (such as PV = nRT) as the first term in a series of powers of a
variable (here, P or V), is common in physical chemistry.
The two expressions above are versions of the virial equation of state (the name comes from the Latin word
for force). The temperature-dependent coefficient B is the second virial coefficient, C is the third virial
coefficient and so on. Their values are determined experimentally. The second coefficient is usually more
important than the third or subsequent terms: that is, B / V >> C / V2
It follows from the discussion above that the greater
Table S2.A8 Second virial coefficients, B (cm3 mol−1)
the magnitude of the second virial coefficient (at a
given temperature), the greater the deviation from Gas T (K)
ideal gas behaviour (see Table S2.A8). Note that the 100 K 273 K 373 K 600 K
values generally become larger in magnitude at lower He 11.4 12.0 11.3 10.4
temperature, indicating that intermolecular forces N2 −160.0 −10.5 6.2 21.7
become more significant and the behaviour of the CO2 −149.7 −72.2 8.1
gases deviates more from that of an ideal gas. The Xe −153.7 −81.7 −19.6
values for helium do not change significantly across
the range of temperatures, indicating the least deviation from ideal gas behaviour, but the larger (and hence
more polarisable) carbon dioxide molecules and xenon atoms have larger values at the intermediate
temperatures than the smaller and less polarisable nitrogen molecules and helium atoms.
An alternative equation of state was proposed by Johannes van der Waals (1837–1923) in 1873, based in part
on some simple assumptions about the behaviour of gas molecules. Firstly he considered the molecules to be
small, hard and impenetrable spheres occupying a total volume b (or nb for n moles of gas). Therefore, the
volume available for a sample of gas to occupy is equal to the volume of the container minus the volume of
the molecules themselves, and the ideal gas law can be modified to give:
𝑛𝑛𝑛𝑛𝑛𝑛
𝑃𝑃 =
𝑉𝑉 − 𝑛𝑛𝑛𝑛
Attractive forces between real gas molecules will tend to reduce the pressure (compared to an ideal gas).
Pressure depends on both the frequency of collisions with the walls of the container and the force of the
collisions. Both the frequency and force depend on the concentration of the gas (n / V), so the reduction in
pressure is proportional to the square of the concentration, which leads to the van der Waals equation of
state:
𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛 2
𝑃𝑃 = − 𝑎𝑎 � �
𝑉𝑉 − 𝑛𝑛𝑛𝑛 𝑉𝑉
This can be rewritten in terms of the molar volume (Vm = V / n):
𝑅𝑅𝑅𝑅 𝑎𝑎
𝑃𝑃 = − 2
𝑉𝑉𝑚𝑚 − 𝑏𝑏 𝑉𝑉𝑚𝑚
Deviation from ideal behaviour becomes evident as the volume is decreased. You can see this clearly in the
output of the simple Python/Glowscript program at https://trinket.io/glowscript/8774cf1976 which plots
pressure versus volume for one mole of an ideal gas (in blue) and one mole of water (in red). You are
encouraged to try changing the temperature in the code to observe how the behaviour of gaseous water
becomes closer to that of the ideal gas at higher temperatures and further from that of the ideal gas at lower
temperatures.
The Geogebra applet at https://www.geogebra.org/m/emnctuxt displays a graph of pressure versus molar
volume, based on the van der Waals equation of state, for an ideal gas and the real gases water, argon,
helium and hydrogen sulfide. The temperature can be adjusted using the slider and the curve for each gas
made visible or hidden by toggling the tick boxes.
How can advances in technology lead to changes in scientific

definitions, e.g. the updated IUPAC definition of the hydrogen bond?
Hydrogen bonds can be regarded as an especially strong dipole–dipole interaction and occur between
chlorine, nitrogen or fluorine in one molecule and hydrogen in another. Chlorine is slightly more
electronegative than nitrogen but its larger atomic radius prevents the formation of an intermolecular force as
strong as that between nitrogen molecules. However, quantum mechanical calculations also suggest some
sharing of a lone pair in nitrogen, fluorine and oxygen. The strength of a hydrogen bond is maximized when
the atoms involved are arranged in a linear manner.
IUPAC has a broader definition of the hydrogen bond than the IB syllabus, stating:
The hydrogen bond is an attractive interaction between a hydrogen atom from a molecule
or molecular fragment X–H in which X is more electronegative than H, and an atom or
group of atoms in the same or a different molecule, in which there is still evidence of
bond formation.
According to the IUPAC definition, hydrogen bonding is not restricted to fluorine, nitrogen and oxygen, but
the interactions with these atoms are usually an order of magnitude stronger than those with heavier elements
such as chlorine and sulfur, so weak hydrogen bonds with these elements are usually only observed in the
solid state.
Experimental evidence for hydrogen bonding is obtained from nuclear magnetic resonance (NMR), ring
currents, neutron diffraction, infrared (IR) spectroscopy and enthalpy change measurements, often performed
in the gas phase.
Neutron diffraction by crystalline solids allows the positions of all atoms, including hydrogen, to be
established accurately in three-dimensional space. If the separation of two electronegative atoms is closer
than the sum of their van der Waals radii, chemists infer the presence of a hydrogen bond.
Why are oxygen and ozone dissociated by different wavelengths of

light?
The relative weakness of the bonds in ozone (O3) compared to the bonds in dioxygen (O2) means that the
bonds of the two molecules are dissociated by ultraviolet radiation of different wavelength (that is different
frequency or energy).
The stratosphere is a layer of the Earth’s atmosphere between 12 km and 50 km above the surface. The lower
regions of the stratosphere are known as the ozone layer because they contain around 90% of atmospheric
ozone at concentrations of around 10 ppm. Ozone levels are maintained through a cycle of synthesis and
decomposition reactions involving oxygen atoms (radicals) and the absorption of energy from UV-C and
UV-B radiation (Table S2.A9).
Table S2.A9 Comparison of oxygen (dioxygen) and ozone (trioxygen)
Oxygen, O2 Ozone, O3
Bonding
Bond order 2 1.5

Bond energy / kJ mol−1 498 364
Dissociation UV-C UV-B
higher energy, shorter lower energy, longer
wavelength radiation wavelength radiation
λ < 242 nm λ < 330 nm
Oxygen dissociation O2 (g) → 2O• (g) UV-A radiation

Ozone synthesis O2 (g) + O• (g) → O3(g) exothermic
Ozone dissociation O3 (g) → O2 (g) + O• (g) UV-B radiation
The dissociation of oxygen molecules into atoms needs ultraviolet radiation of a shorter wavelength than the
decomposition of ozone molecules. By absorbing much of the higher energy radiation from the Sun, these
reactions protect the surface of the Earth from the highly damaging effects of UV-B and UV-C radiation
which include skin cancer and cataracts. Most of the ultraviolet radiation reaching the Earth’s surface is the
least harmful and lower energy UV-A form(Figure S2.A37).
Figure S2.A37 Absorption of UV-B and UV-C in the stratospheric ozone–oxygen cycle
Calculations
The wavelength of UV light required dissociate oxygen and ozone molecules can be calculated:
1 mole of O=O bonds in an oxygen molecule requires 498 kJ to form oxygen atoms.
1 O=O bond requires (498 × 103 J mol-1) ÷ (6.02 × 1023 mol− 1) J to dissociate
So the energy a photon must have to dissociate one O=O bond = (498 × 103 J) ÷ (6.02 × 1023 mol− 1) = 8.27 x
10-19 J
Using Planck’s relationship, E = hf (where f is the frequency in s−1 or Hz, E is the energy of the
electromagnetic radiation in J, and h is Planck’s constant, 6.63 × 10−34 J s), and the wave equation, c = f × λ
(where c is the speed of light = 3.00 × 108 m s−1, f is the frequency in s−1 or Hz and λ is the wavelength in m)
gives:
E = hf = hc / λ
so λ = hc / E
λ = (6.63 × 10−34 J s) × (3.00 × 108 m s−1) × (6.02 × 1023 mol−1) ÷ (498 × 103 J mol-1)
= 2.42 × 10−7 m = 242 nm
1 mole of oxygen–oxygen bonds in an ozone molecule requires 363 kJ to form oxygen atoms, so the required
wavelength is given by:
λ = hc / E
= (6.63 ×10−34 J s) × (3.00 × 108 m s −1) × (6.02 × 1023 mol−1) ÷ (363 ×103 J mol-1)
= 3.30 × 10−7 m = 330 nm
How does the resonance energy in benzene explain its relative

unreactivity?
R2.2 How fast? The rate of chemical change
The resonance energy is a measure of how much more stable a compound with delocalized pi electrons is
than it would be if its pi electrons were localized.
The enthalpy change of hydrogenation of cyclohexene, a compound with one localized carbon–carbon
double bond, has been determined experimentally to be −120 kJ mol−1. We would, therefore, expect the
enthalpy change for the hydrogenation of “cyclohexatriene,” a hypothetical compound with three localized
carbon–carbon double bonds, to be three times that of cyclohexene: −360 kJ mol−1. However, the
experimentally determined enthalpy of hydrogenation of benzene is −208 kJ mol−1 – the reaction is much
less exothermic than expected (Figure S2.A38).
Figure S2.A38 Comparison of the enthalpy of hydrogenation of the Kekulé structure (“cyclohexatriene”) and the
actual structure of benzene (resonance hybrid)
This indicates that approximately 150 kJ more energy is required to break the π bonds in one mole of
benzene than is needed to break the three π bonds in one mole of the hypothetical cyclohexatriene molecule.
The difference between the two values is known as the resonance energy.
More evidence for the stabilization of benzene by resonance comes from a comparison of its enthalpy of
formation with that calculated using standard bond enthalpies. Consider the equations below:
6C(graphite) + 3H2(g) → C6H6(g) ∆Hf ⦵ = +83 kJ mol−1

6C(g) → 6C(graphite) ∆Hr⦵ = −4296 kJ mol−1
6H(g) → 3H2(g) ∆rH⦵ = −1308 kJ mol−1
Applying Hess’s Law to combine these yields:
6C(g) + 6H(g) → C6H6(g) ∆rH⦵ = −5521 kJ mol−1
If we instead assume the product of the reaction above to be the hypothetical cyclohexatriene molecule:
6C (g) + 6H (g) → (g)
we can sum the (negative) bond enthalpies of six C–H, three C–C and three C=C bonds to obtain an enthalpy
change of −5364 kJ mol−1.
This again indicates that benzene is stabilized by slightly more than 150 kJ mol−1compared to the cyclic
triene (Figure S2.A39).
Figure S1.A39 Comparison of the experimental enthalpy

of formation of gaseous benzene with that of gaseous
cyclohexatriene
What are the structural features of benzene that favour it undergoing

electrophilic substitution reactions?
A benzene molecule consists of a planar ring of six carbon atoms each of which is bonded to a hydrogen
atom. The bond angles within the ring are all 120°. This suggests that the carbon atoms in the ring are all sp2
hybridized, with an unhybridized p orbital remaining on each carbon. It is the electrons in the unhybridized p
orbitals that overlap to form the delocalized cloud of π electrons that give rise to the resonance stability of
benzene. The key features of a molecule that give rise to aromaticity are:
• a delocalized, conjugated π system (usually an arrangement of alternating single and double bonds)
• a planar structure
• atoms arranged in one or more rings.
Evidence for the delocalization of the π electrons in the ring comes from measurements of so-called aromatic
ring currents. If a magnetic field is applied in a direction perpendicular to the plane of a benzene ring, a ring
current is induced in the delocalized π electrons (Figure S2.A40).
These ring currents have relevance to NMR spectroscopy, as they significantly influence the chemical shifts
of 1H nuclei in aromatic molecules such as benzene.
Figure S2.A40 An induced ring current in a benzene ring
The high electron density associated with the delocalized π cloud in a benzene ring explains its tendency to
react with electrophiles (derived from the Greek meaning ‘electron loving’). This is similar to how an alkene
reacts via its π bond electrons. An electrophile is a Lewis acid since it reacts by accepting a pair of electrons
from a nucleophile (derived from the Greek meaning ‘nucleus loving’); that is, a species that can donate an
electron pair towards a positively charged centre.
Both alkenes and benzene react in the first instance by addition of an electrophile, E+.. After the addition of
the electrophile, alkenes undergo addition by bonding to X− but, instead of completing the addition, the
benzene intermediate loses a proton to form a substitution product, restoring the aromatic stability of the
delocalized π electron cloud (Figure S2.A41).
Figure S2.A41 Curly arrow mechanism for a general electrophilic substitution reaction of benzene,
where E denotes the electrophile
An important example of electrophilic substitution is the nitration of benzene, shown in Figure S2.A42. The
electrophile is a nitronium ion, NO2+, formed via the protonation of nitric acid by sulfuric acid and
subsequent loss of a water molecule. In the first step, a pair of electrons from the π cloud of the benzene ring
forms a bond to the nitrogen of the nitronium ion, which produces a positively charged intermediate.
Subsequent loss of an H+ ion restores six electrons, and hence aromatic stability, to the benzene ring.
Figure S2.A42 Nitration of benzene via electrophilic substitution
S2.3 The metallic model
What experimental data demonstrate the physical properties of metals,

and trends in these properties in the periodic table?
Inquiry processes Inquiry process 2 Interpreting results
It should be noted that some properties of metals are microstructure-insensitive, such as density, modulus
and melting point. However, some properties of metals are microstructure-sensitive, such as tensile strength,
hardness, thermal conductivity and electrical conductivity. The microstructure refers to the size and
arrangement of the grains of the metal.
Table S2.A9 shows that, for the metals in the fourth period, density increases from potassium to copper, in
line with the increase in atomic mass and decrease in atomic radius across the period. Similarly, there is a
general decrease in molar volume from potassium to nickel.
The molar volume depends on the packing-density of atoms in the crystal (and thus on the crystal structure),
but the data shows that the position in the period has a much greater influence: in any row, the atomic
volume is a minimum in the middle.
As the atomic number increases across a row, the nuclear charge increases and this charge is incompletely
shielded by the inner shells (core electrons), causing the valence shell to contract. The imperfect shielding is
a maximum in the middle of the period, leading to the minimum in atomic volume.
Table S2.A10 Physical properties of metals in period 4
Thermal conductivity /
Young modulus / GPa
thermal expansion / ×
Coefficient of linear
Molar volume / cm3
Rigidity or shear
Mineral (Mohs)
Reflectivity / %
modulus / GPa
Solid density /
× 10−8 W m
Resistvity /
W m−1 K−1
hardness
10−5 K−1
g cm−3
Metal
K 856 45.94 – 1.3 0.4 7.5 100.0 – –

Ca 1550 26.20 20 7.4 1.8 3.4 200.0 2.23 –
Sc 2985 15.00 74 29.0 – 55.0 16.0 1.02 –
Ti 4507 10.64 116 44.0 6.0 40.0 21.9 0.86 –
V 6110 8.32 128 47.0 7.0 20.0 30.7 0.84 –
Cr 7140 7.23 279 115.0 8.5 12.7 94.0 0.49 –
Mn 7470 7.35 198 – 6.0 144.0 7.8 2.17 –
Fe 7874 7.09 211 82.0 4.0 10.0 80.0 1.18 65
Co 8900 6.67 209 75.0 5.0 6.0 100.0 1.30 67
Ni 8908 6.59 200 76.0 4.0 7.2 91.0 1.34 72
Cu 8920 7.11 130 48.0 3.0 1.7 400.0 1.65 90
Zn 7140 9.16 108 43.0 2.5 6.0 116.0 3.02 80
Ga 5904 11.8 – – 1.5 14.0 29.0 12.00 –
The tensile strength (as measured by the Young’s modulus and rigidity or shear modulus) and hardness (as
measured by the Mohs scale which is a qualitative measure of scratch resistance) of the metals tend to
increase up to chromium and decrease thereafter. The Young’s and rigidity or shear modulus are elastic
parameters, which relate to how easy it is to stretch or deform an interatomic bond, whereas the hardness is
related to the strength, or how easy it is to break bonds.
The trends in other properties such as electrical resistivity (inversely related to electrical conductivity) and
thermal conductivity are not so simple and are consequently harder to fully explain without recourse to
complex quantum mechanical considerations.
However, a simple model (due to the physicist Nevill Mott) assumes that for most of the first-row transition
metals, it is the 4s electrons which are delocalized and mainly responsible for the electrical and thermal
conductivity. In metallic bonding of these metals, the 3d and 4s orbitals overlap significantly and they should
both be considered but Mott suggests that the 3d electrons move much more slowly, due to their higher
effective mass, and thus contribute less to conductivity.
What are the features of metallic bonding that make it possible for
metals to form alloys?
There are two main structural types of alloys: intermetallic alloys and solid solutions.
An intermetallic alloy, such as the sodium-mercury amalgam, NaHg2 used as a reducing agent, is a
compound with a fixed composition and definite properties.
A solid solution is one element dissolved in the other. Due to the nature of metallic bonding (fixed cations
and delocalized valence electrons), and the close packed structures they usually adopt, it is easy to introduce
other metal atoms into the lattice The sea of delocalized electrons will bond all the metal atoms together even
if the metal atoms are of slightly different sizes. The original two crystalline solids form a new crystalline
solid, or crystal lattice. The occupation of crystal lattice sites by the atoms of the alloy is essentially random.
The relative percentages of the metals can be varied to modify the properties of a metal to suit different
purposes: for example, bronze is a solid solution of copper and tin in which the percentage of tin can vary
from 1% to 40%.
Solid solutions can be classified as either substitutional
or interstitial (Figure S2.A43), depending on the atomic
arrangement. In a substitutional alloy, such as brass or
bronze, the atoms from the dissolved metal occupy the
same sites as those of the other metal. In interstitial
alloys, atoms of one element are found in the gaps
(interstices) of the lattice of the other. Stainless steel is
a combination of interstitial and substitutional alloys:
carbon atoms fit into the interstices but some of the iron
atoms are replaced with nickel and chromium atoms.
Figure S2.A43 Solid solution structures:
(a) substitutional and (b) interstitial alloys
Most alloys contain solid solutions, but also have other

phases: they are heterogeneous. Steels are iron alloys
containing up to 2% carbon that can have a variety of
phases which differ in, for example, their packing of
iron atoms. More carbon can dissolve in the high
temperature form of iron (austenite) than in the low
temperature form (ferrite). Carbon atoms occupy
interstitial sites in both austenite and ferrite. If solid
austenite steel is cooled slowly, a banded structure
(pearlite) consisting of layers of almost pure iron
(ferrite) and iron carbide (Fe3C, cementite) forms Figure S2.A44 Schematic diagram of the
(Figure S2.A44). pearlite steel microstructure
What trends in reactivity of metals

can be predicted from the periodic table?
The reactivity of metals can be observed in chemical reactions such as:
• the formation of oxides with oxygen
• the formation of halides with halogens
• how readily they displace hydrogen from solutions of dilute acid
• how readily they displace the ions of a less reactive metal from solution.
In chemical reactions, metals become oxidized by losing electrons so trends in the reactivity of metals should
follow trends in ionization energies of the valence electron(s) and reduction potential. In general, ionization
energies decrease when descending a group and increase across a period; reduction potentials become more
negative down a group (indicating a greater tendency of the metal to become oxidized), and less negative
across a period. Therefore, when considering the metals in a specific group of the periodic table, we can
predict that reactivity with oxygen, halogens and dilute acid (or water) is likely to increase down the group.
A metal in a given group would be expected to displace the cations of a metal higher in the same group from
aqueous solution; however, the highly reactive metals in groups 1 and 2 do not undergo such displacement
reactions because they react directly with water.
When considering the sequence of metals in a particular row of the periodic table, in general reactivity with
oxygen, halogens and dilute acid will decrease across the period.
Why is the trend in melting points of metals across a period less evident
across the d-block?
Melting point trends are always a lot more complicated than trends in boiling point because there is still quite
strong bonding between particles in the liquid state. As such, melting point trends reflect the degree to which
the strength of this bonding is dependent on a fixed crystal structure, not necessarily the strength of the
bonding.
The trends in melting points of the d-block elements are complicated (Figure S2.A45). In moving along the
first row of the d-block (Sc to Zn), the melting points first increase from scandium to vanadium, decrease
from vanadium to chromium and then rise to iron then decrease regularly towards the end of the period.
This trend cannot be explained by the electron sea model but can be explained using band theory based on
atomic orbitals and a knowledge of their metallic lattice structures.
• The increase in melting point for the early elements in the transition series corresponds to the
increase in the number of 3d and 4s electrons that occupy the bands responsible for metallic bonding.
• After about the middle of the series, additional electrons have to occupy higher energy states so the
bonding between atoms becomes weaker.
• By the time the end of the series is reached, the filled d sublevel is no longer a major factor in the
metallic bonding.
• The half-filled and filled d electron configurations that occur at manganese and zinc have a
significant effect due to their stable electron configurations (because exchange energy effects)
making the release of valence electrons energetically unfavourable.
Iron, cobalt and nickel are ferromagnetic which strengthens the strength of the metallic bonding (via a
quantum effect).
Figure S2.A45 Melting and boiling points of the first-row 3d-block metals
S2.4 From models to materials
What are the limitations of discrete bonding categories?

To quote Bryce Crawford (1953): “The nature of the chemical bond is at the heart of all chemistry.”
The van Arkel diagram (bonding triangle) recognizes that the elements and binary compounds exhibit three
extreme forms of bonding: metallic, ionic and covalent. However, this cannot be a complete description
since covalently bonded substances take two very different forms: covalent network structures (such as
diamond, silicon dioxide and silicon) and simple or molecular covalent substances (such as iodine and
methane) where individual molecules interact via weak intermolecular forces. Bond type is only one of
several factors which determine overall structure type. Considering this extra dimension leads to the
tetrahedron of structure and bonding types shown in Figure S2.A46.
Figure S2.A46 The triangle of bonding and tetrahedron of structure, bonding and material type
Figure S2.A47 shows the various chemical

models and bonding theories mapped onto the
bonding tetrahedron. Band theory provides
models for metals and semiconductors; ionic
substances use lattice models; network covalent
materials are modelled either by the sea of
electrons model (for metals) or molecular orbital
(MO) theory; and MO or valence shell electron
pair repulsion (VSEPR) theory can be used to
model molecular substances.
Humans have a tendency to think in terms of
dichotomous (either–or) extremes. This can be
Figure S2.A47 Truncated tetrahedron of structure,
very useful when classifying large numbers of
bonding and material
different substances and is what we do if we
consider electronegativity alone and use it with
the bonding triangle to decide if bonding is ionic, covalent or metallic. However, a bonding category is an
idealization. Any chemical bond is the result of several physical mechanisms present in different
percentages. A dichotomous approach to understanding the nature of chemical bonds does not take into
account the properties of polar covalent substances (including those with a polymeric structure) and ionic
substances with covalent character.
When considering a wide range of chemical substances, dichotomous thinking can be counterproductive as
chemical substances cannot always be neatly categorized into a small number of groups. It is therefore
necessary to discern when a more critical (dialectical) mode of thinking is required. It may be helpful to
introduce more groups, such as semiconductors and metalloids, or even new classifications, for example,
metavalent bonding for substances such as GeSe and SnTe which are electrical conductors and have
particular thermoelectric properties.
How do the trends in properties of period 3 oxides reflect the trend in

their bonding?
Table S2.11shows selected properties of the oxides of the period 3 elements. Where two are shown, the first
is the ‘highest’ oxide of the element: that is, the one in which the element is in its highest oxidation state.
Table S2.A11 Physical and chemical properties of the oxides of the period 3 elements.
Metal
Oxide
Na Mg Al Si P S Cl
Formula Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
[Na2O2] [P4O6] [SO2] [Cl2O]
[ClO2]
Standard state solid solid solid solid solid liquid liquid
[solid] [solid] [gas] [gas]
[gas]
Element +1 +2 +3 +4 +5 +6 +7
oxidation state [+1] [+3] [+4] [+1]
[+4]
Melting point / 1132 2852 2072 1710 340 17 −92
°C [460] [24] [−72] [−121]
[−59]
Boiling point / 1950 3600 2977 2230 360 45 82
°C [657] [173] [−10] [2]
[11]
Electrical high High High very low nil nil nil
conductivity [high] [nil] [nil] [nil]
(molten) [nil]
Bonding / ionic Ionic ionic (some giant molecular molecular molecular
structure covalent covalent covalent covalent covalent
character) network
Product of NaOH Mg(OH)2 no reaction no H3 PO4 H2 SO3 HClO4
reaction with reaction [H3 PO3 ] [H2 SO4 ] [HClO]
water [5HClO3
+ HCl]
Products of NaCl MgCl2 AlCl3 no no no no
reaction with H2 O H2 O H2 O reaction reaction reaction reaction
HCl(aq)
Products of no no Na[Al(OH)]4 Na2 SiO3 Na3 PO4 Na2 SO3 NaClO4

reaction with reaction reaction H2 O H2 O [Na2 SO4 ] [NaOCl]
NaOH(aq) H2 O [NaClO3
+
NaClO2]
H2 O
Nature basic Basic amphoteric acidic acidic acidic acidic
Inspection of the table shows that, as period 3 is crossed from left to right, the oxides progress from ionic to
covalent. The difference in electronegativity between the period 3 element and oxygen is high at the left-
hand side and decreases going across the period.
The ionic oxides of sodium, magnesium and aluminium possess high melting and boiling points and are
excellent conductors of electricity in the molten state because the ions become mobile when the oxide melts,
and so can conduct electrical charge. The electrolysis of aluminium oxide (using small amounts of molten
cryolite, Na3AlF6, to lower the melting point of aluminium oxide) forms the basis of the Hall–Heroult
process for refining aluminium.
The oxides of sodium and magnesium are basic, and both react with water to produce alkaline solutions. In
addition, they both react with hydrochloric acid to produce a neutral salt and water.
Aluminium cations and oxide anions are both small and highly
charged, therefore Al2O3 (commonly known as alumina) has strong
bonding and is insoluble in water. Despite being a metal oxide, the
bonding in alumina has some covalent character. Aluminium oxide has
basic oxides to its left and acidic oxides to its right but is itself
amphoteric, reacting with both HCl and NaOH. A common crystalline
form of aluminium oxide is corundum (α-Al2O3, Figure S2.A48). The
gemstones ruby and sapphire are varieties of this that contain coloured
transition metals as impurities. Because of its high melting point and
hardness, corundum is often used as a refractory (heat-resistant)
material in kilns and as an abrasive for scratching and polishing other
hard materials.
Figure S2.A48 An impure sample
Silicon dioxide (commonly known as silica or sand) has a giant
of corundum: a very hard,
covalent network structure and, hence, a very high melting and boiling crystalline form of the ionic
point. Due to the absence of ions or delocalized electrons in its compound aluminium oxide
structure, silica does not conduct electricity. It is insoluble in water and
is an acidic oxide. Its reaction with sodium
hydroxide to form sodium silicate, Na2SiO3 (2Na+
SiO32−), is the key reaction in the manufacture of
glass. Glasses make up a class of ceramics which
are not crystalline. They are amorphous, meaning
the particles are arranged in an irregular way.
Figure S2.A49 shows a two-dimensional
representation of a glass modified by the addition
of cations of a metal, M (in practice, this is often
Na+). The bonding in the glass network is covalent
but the bonding between the metal ions and Figure S2.A49 Structure of glass
negatively charged oxygen atoms in the network is
ionic. The metal lowers the melting point and reduces the hardness.
The oxides of phosphorus, sulfur and chlorine are all simple molecular covalent substances and, therefore,
have comparatively low melting and boiling points and are non-conductors in the molten state. All are acidic
oxides that react with bases such as sodium hydroxide to produce a salt and water.
Why do composites like cement, which are made from both ionic and
covalently bonded components, have unique properties?
S2.3 The metallic model
A composite material is that one that is composed
of two or more different materials bonded together
with one serving as the supporting matrix
surrounding particles or fibres of the other. Well-
known composites include cement, concrete,
foams, fibre-reinforced plastics and laminates. A
very early example of a natural composite was
straw and clay used to make huts.
Composite materials are heterogeneous mixtures.
In a composite material, the properties of the
Figure S2.A50 The arrangement of fibres of
components combine to give a material which is poly(ethene) in a resin matrix
more useful for a particular purpose than the
individual components.
Cement is used as a bonding agent. When combined with fine sand it
forms mortar, which is used to bind bricks or stones together.
Adding gravel (small stones) gives concrete. Reinforced concrete
contains a mesh work of steel rods over which the mixture is poured.
It is used in the construction of bridges and large buildings. Portland
cement is a white cement made by strongly heating a fine aqueous
sludge of limestone (calcium carbonate, CaCO3) and silica (silicon
dioxide, SiO2). Clay (Al2O3.2SiO2.2H2O) or shale is also added.
When a cement mixture is heated to about 1500 °C in a kiln, the Figure S2.A51 Palace Assembly
water evaporates and high-temperature reactions produce calcium building, Chandigarh, India is
silicates, calcium aluminates and calcium aluminoferrites. These made from concrete
crystallize from the melt and sinter together into pebbles (clinker) as
the products of the kiln cool. Each of these minerals has various foreign ions substituted into lattice positions
and some of these are important in stabilizing the reactive crystal structures which give cement its hydration
characteristics. In Portland cement, the clinker is ground to a fine powder with powdered gypsum
(CaSO4.2H2O).
Cement powder is mixed with water to form cement paste. Acid–base chemistry then leads to the dissolution
of minerals from grains of the powder and the precipitation of new hydration products (Figure S2.52). The
hydration rate of the minerals varies leading to the development of a complex microstructure with particles
and pores of varying sizes, which contributes to the strength of the cement. This microstructure changes and
develops as different hydration products are precipitated. Initially, Na+ and K+ ions are released into the
water in the mix making it alkaline so that the silicate and aluminate in solution are in the form of ions
H3SiO4− , H2SiO42− and Al(OH)4 −. The release of hydrated calcium ions provides the Lewis acid with which
the hydrated silicates (bases) react to form calcium silicate hydrate species. The resulting amorphous calcium
silicate hydrate precipitate is known as C-S-H and is the principal binding phase in Portland cement.
Another reaction occurs in Portland cement because of the gypsum present. Small ettringite crystals
containing sulfate ions form quickly and coat the cement particles. Although these are not large enough to
bridge the gaps and bind the particles, they affect the type and location of hydration, promoting the
formation of C-S-H and slowing the rate at which the cement hardens. The C-S-H gel has a very large
surface area and contains a relatively large amount of water which contributes to the binding.
Tricalcium silicate, in the form of alite (an impure form of Ca3SiO5), is another major component of cement.
It hardens by absorbing water to form long needle-like crystals of hydrated calcium silicate
3CaO.SiO2.2H2O. Smaller needles then fill the gaps between the particles. Ca(OH)2, which forms plates, is
also important.
The interactions between different components of the mixture act to strengthen the matrix overall.
Why are alloys more correctly described as mixtures rather than as

compounds?
Themes S1.1 Introduction to the particulate nature of matter
While some well-known alloys have just two constituents (for example, copper and zinc in brass, copper and
tin in bronze, aluminium and copper in duralumin, iron and carbon in steels), most alloys have a number of
additions–there may be ten or more in some steel grades–most at very low levels. There can also be a whole
host of trace elements and contaminants.
Metals are usually completely soluble in one another when they are
liquid, but not when solid. When a small amount of alloying element is
added to a metal, it will usually be soluble in the liquid and will then
remain in solid solution when the alloy freezes. Solid solutions can either
be substitutional or interstitial (Figure S2.A53).
• In substitutional solid solutions, the atoms of the solute elements
substitute for those of the parent on the atomic sites of the parent
metal crystal.
• In interstitial solid solutions, the smaller solute atoms fit into the Figure S2.A53 The metal
interstices (spaces) between the atoms of the parent-metal. atoms in a solid solution
Substitutional solid solutions are much more common. The most

important example of an interstitial solid solution is that of carbon in iron giving rise to steels.
Many metallic alloys can be regarded as a homogeneous mixture of metallic elements existing in one solid
phase, whose composition of its components can be varied.
The formation of a solid solution is a physical process rather than a chemical one making the alloy a mixture
rather than a compound.
What functional groups in molecules can enable them to act as

monomers for addition reactions?
Most addition polymers are formed from unsaturated monomers (usually containing a single carbon-carbon
double bond). The pi electrons in the carbon-carbon double bond make the functional group relatively
reactive and facilitate addition polymerization. Addition polymerization can also occur with dienes, such as
the formation of natural rubber from isoprene (2-methylbutadiene).
Unlike condensation polymerization, in which a small molecule is eliminated when the monomers link
together, in addition polymerization all the atoms in the monomers are retained in the polymer product.
Addition polymerization is also referred to as chain-growth polymerization, as it proceeds via a free-radical
chain mechanism, which is similar in many respects to the ultraviolet-initiated reaction of a halogen with an
alkane (see Reactivity 3.3). Organic peroxides (Figure S2.A54) are often used to initiate addition
polymerization, as they contain a weak O–O single bond that is readily broken by heat or ultraviolet light.
Figure S2.A54 Mechanism of the addition polymerization of an alkene
The propagation steps lead to an increase in the length of the carbon chain, and termination occurs when two
radical chains bond together covalently. Different polymers can be produced by changing the groups
attached to the double-bonded carbons of the alkene monomer.
A similar reaction can occur when an alkyne is used as the monomer, but the resulting polymer is
unsaturated rather than saturated. The polymer contains alternating single and double bonds (it is a
conjugated polyene) but, due to resonance, the pi electrons become delocalized along the entire length of the
polymer chain and such polymers are electrically conductive. In 2000 the Nobel Prize was awarded to the
chemists Alan MacDiarmid, Alan Heeger and Hideki Shirakawa for their work on the development of
conducting polymers.
Addition polymers may also be formed from cyclic molecules via a ring-opening process. This is a form of
addition polymerization (but not involving addition reactions as observed with alkenes and substituted
alkenes), in which the terminal end of a polymer acts as a reactive centre. The reaction is typically driven by
the release of ring strain. This is how of polyethylene glycol is formed from ethylene oxide (an epoxide)
(Figure S2.A55).
Figure S2.A55 Polymerization of ethylene oxide to form polyethylene glycol
The polyamide nylon 6 (Figure S2.A56) is formed via the ring-opening polymerization of ε-caprolactam and,
although the product resembles a typical polyamide, it is an addition polymer and not a condensation
polymer.
Figure S2.A56 Formation of the addition polymer nylon 6 from the cyclic monomer ε-caprolactam
Why is the atom economy 100% for an addition polymerization

reaction?
The concept of atom economy is derived from the principle of green chemistry. Atom economy is a measure
of the proportion of reactants that become useful products.
% atom economy = molar mass of desired product × 100%

molar mass of all reactants
In an ideal reaction, all reactant atoms end up within the useful product molecule and no waste is produced.
Inefficient, wasteful reactions have a low atom economy. Efficient processes have high atom economy and
are important for sustainable development. They conserve natural resources and create less waste.
Green chemistry is the sustainable design of chemical products and processes. It aims to minimize the use
and generation of chemical substances that are harmful to human health or the environment. Chemists design
reactions with the highest possible atom economy in order to minimize the environmental impact and reduce
the consumption of raw materials and energy.
High atom economy is achieved by addition reactions while lower atom economies are typical for
substitution and condensation reactions. The production of addition polymers also represents 100% atom
economy since all of the reactant monomers end up in the polymer product.
Figure S2.A57 Atom economy calculation for polyethene
What are the structural features of some plastics that make them
biodegradable?
Polymers are mostly quite resistant to biodegradation because they are hydrophobic (due to the presence of
–CH2– units) and the chains are long and highly entangled, making the interior less accessible to chemical or
biochemical reactions.
For a polymer to be biodegradable it needs to be sufficiently hydrophilic that enzymes in solution can act on
its surface, and it needs to have functional groups in the chain which can be cleaved, either hydrolytically or
enzymatically, to give molecules small enough to cross the cell membrane.
Proteins and carbohydrate polymers, such as starch, are biodegradable because nature has evolved enzymes
which can cleave the amide bond in proteins and the glycosidic link between sugars. Because all natural
amide bonds are between alpha-amino acids (2-amino acids), other polyamides, such as nylons, are resistant
to biodegradation. Nylons are also more hydrophobic than proteins.
The vast majority of synthetic biodegradable polymers are polyesters. Polyethene benzene-1,4-dicarboxylate
or poly(ethylene terephthalate) (PET) (Figure S2.A58) is commonly used as a container for carbonate drinks.
A material like PET is not biodegradable because it is hydrophobic
and contains a benzene ring in its repeating sub-unit. If some of the
aromatic rings are replaced by aliphatic units (–(CH2)n–) the melting
point drops and biodegradability increases. Partially aliphatic
polyesters are commercially viable and have been developed as
biodegradable materials. Wholly aliphatic polyesters are typically
biodegradable but not much use as their melting points are too low. Figure S2.A58 Structure of PET
A good example of a biodegradable polyester is poly(lactic acid) or
polylactide (PLA) which is a thermoplastic synthesized by the
condensation polymerization of lactic acid made from corn syrup.
PLA is an aliphatic polyester (Figure S2.A59). It is quite resistant to
biodegradation at room temperature, but it biodegrades easily in
commercial compost conditions. Manufacturers use PLA because it
is cheaper to synthesize than other biodegradable plastics: it is bio-
derived and corn farming subsidies make feedstock cheap in many
places. In addition, PLA is biocompatible so it can be used in Figure S2.A59 Structure of PLA
biomedical applications, such as for plates and screws that will
eventually be degraded and absorbed by the body instead of requiring another operation to remove. PLA is
also the most widely used plastic filament material in 3D printing.
Carbon chain polymers are very resistant to biodegradation but will eventually degrade through oxidation
reactions.
Natural rubber, an addition polymer of the diene isoprene, biodegrades oxidatively so, for applications,
antioxidants are added to prevent the surface reacting with molecular oxygen.
What functional groups in molecules can enable them to act as

monomers for condensation reactions?
In principle, any pair of functional groups which can couple could be used in a step-reaction polymerization.
• Functional groups for the formation of nylon are amine and carboxyl or amine and diacyl chloride.
• Functional groups involved in the formation of polyesters are hydroxyl and carboxyl.
• Functional groups involved in the formation of polysaccharides are hydroxyl groups.
• The formation of nucleic acids involves hydroxyl groups on phosphate groups and sugar
(monosaccharide) residues.
S3.1 The periodic table
How has the organization of elements in the periodic table facilitated the
discovery of new elements?
Themes S1.2 The nuclear atom
Dimitri Mendeleev (1834–1907)
(Figure S3.A1) was a Russian chemist
who arranged the known chemical
elements into a table in order of
increasing relative atomic mass (then
known as atomic weight) to show
chemical periodicity.
He left gaps for undiscovered elements,
making predictions for the chemical
and physical properties of five of these
based upon the properties of
neighbouring elements. His predictions
were shown to be accurate following
the discovery of germanium
(metalloid), gallium (p block metal),
scandium (d block metal), francium
(alkali metal) and technetium (d block
Figure S3.A1 Miniature set including a stamp (in the middle part)
metal) (Table S3.A1).
commemorating the publication of Mendeleev’s first periodic table in 1869
Table S3.A1 A selection of predictions about germanium made by Mendeleev
Property Predicted properties of eka-silicon, Properties of germanium, Ge

Es (predicted by Mendeleev in 1871) (discovered by Winkler in 1886)
Relative atomic mass 72 72.6
Density 5.5 g cm−3 5.47 g cm−3
Appearance Dirty grey metal Lustrous (shiny) grey metal
With air Will form a white powder, EsO2, Gives a white powder, GeO2,
on heating on heating
With acids Slight reaction only No reaction with dilute sulfuric or
hydrochloric acid
Properties of oxide, MO2 Very high melting point, Very high melting point,
4.7 times denser than water 4.7 times denser than water
Properties of chloride, MCl4 Liquid, boiling point less than 100 °C Liquid, boiling point 86 °C
After all the ‘gaps’ are filled, there are 81 elements in the periodic table that have at least one stable isotope.
Nuclear stability is controlled by the same general principles as chemical stability: the potential energy of the
system tends to a minimum and, at equilibrium, there is a balance between attractive and repulsive forces. In
the nucleus:
• Protons, being positively charged, repel each other as a result of electrostatic repulsion.
• Nucleons (protons and neutrons) attract each other by the strong nuclear force which, at very short
distances, is much stronger than the electrostatic force.
Protons and neutrons, like electrons, tend to form pairs and make up shells inside the nucleus. Their energies
are quantized, again like electrons, meaning they can only have specific and fixed amounts of energy.
For the light elements with low atomic numbers, electrostatic repulsion between protons is minimized by the
presence of a similar number of neutrons in the nucleus. Neutrons increase the number of attractions through
the strong nuclear force, but do not add to electrostatic repulsion. Up to calcium (atomic number 20), the
numbers of protons and neutrons are approximately equal, so the mass number is about twice the atomic
number. After calcium, the electrostatic repulsion resulting from the increased number of protons can only
be counterbalanced by making the neutron to proton ratio greater than 1.
In nuclei with more than 83 protons (atomic number greater than that of bismuth), the electrostatic repulsion
between the protons becomes so great that the nuclei undergo radioactive decay. All the elements beyond
uranium (atomic number 92) are synthesized by nuclear reactions, often bombardment. The newly prepared
elements have highly unstable nuclei decay rapidly. The chemical properties can be predicted from trends in
the periodic table (for example, element 118 was named oganesson as it should be a noble gas) but with less
accuracy due to the effects of relativity.
Theoretical calculations suggest there may be new superheavy elements (Figure S3.A2) to be discovered in
an ‘island of stability’, where the elements may have at least one isotope with a relatively long half-life.
Figure S3.A2 A plot of neutron number versus proton number showing where stable and
unstable nuclei are found. So-called magic proton and neutron numbers, at which nuclei have
enhanced stability, are indicated by red lines.
Why are simulations and online reactions often used in exploring the
trends in chemical reactivity of group 1 and group 17 elements?
Tools Tool 2 Use computer modelling
Inquiry processes Inquiry process 2 Designing
The elements of groups 1 and 17 have valence electron configurations of ns1 and np5, respectively.
Group 1 elements (alkali metals) react readily via loss of the ns1 electron to obtain an electron configuration
that is isoelectronic with the noble gas in the preceding period and are therefore strong reducing agents.
Reactivity increases as group 1 is descended since the valence electron becomes less tightly bound due to the
increase in the number of electron shells and shielding. For this reason the reactions of group 1 elements
with, for example, oxygen and water, become more violent as the group is descended. Whilst the reactions of
small quantities of lithium and sodium (and, in some countries, potassium) with water may be demonstrated
in the chemistry laboratory, precautions such as the use of a safety screen must be taken.
When an alkali metal is added to water there are two key stages to the explosion. First there is an electron
transfer from the alkali metal to a water molecule which produces hydrogen gas and aqueous hydroxide ions.
Secondly, the hydrogen mixes with air. If an explosive mixture of hydrogen and oxygen is produced, the heat
from the first part of the reaction may cause ignition and flames will be observed above the water.
One mole of hydrogen gas is produced per two moles of alkali metal. Because caesium has a relative atomic
mass of 132.91 compared to 6.94 for lithium, one gram of caesium produces only about a twentieth of the
amount of hydrogen evolved by one gram of lithium, and this explains why the reactions of caesium and
rubidium are less violent than might be expected. Even so, these elements are too hazardous to handle in a
school laboratory.
The element francium is highly radioactive; its most stable isotope has a half-life of only 22 minutes, and it
is estimated that only 20–30 grams of the element exist in the Earth’s crust at any given time.
Group 17 elements (halogens) react by gaining an electron and become isoelectronic with the adjacent noble
gas element (to their right). They therefore act as oxidizing agents. Reactivity of the halogens increases up
the group as the electronegativity of the element increases, with fluorine being the most electronegative, and
hence most reactive element in the group.
Both fluorine and chlorine gases are highly toxic at low concentrations. Pure bromine is less toxic but as
little as 100 mg of the pure liquid is lethal. Iodine vapour is somewhat toxic and can cause irritation to the
lungs and eyes, but solid iodine and its aqueous solution (and also dilute aqueous solutions of bromine and
chlorine water) can be used in the laboratory in small quantities with due attention to safety: safety glasses,
gloves, lab coat and use of a fume cupboard. Fluorine can only be prepared by electrolysis of molten
fluorides. Fluorine is highly reactive and combines directly with all non-metals except nitrogen, helium,
neon and argon..
The element astatine is radioactive. The longest-lived isotope, 210At, has a half-life of about 8 hours and
hence it is highly dangerous. As with francium only minute quantities (about 25 g) are thought to exist on
Earth at any given time. Only a small number of atoms of the recently discovered tennessine (Z = 117) have
been detected and its isotopes have half-lives of much less than a second; it is highly radioactive.
As a consequence of the safety issues outlined above, the reactions of the alkali metals and halogens are
often explored using online simulations or video clips.
How do differences in bonding explain the differences in the properties

of metal and non-metal oxides?
The acid–base nature of an oxide is related to the position of the element forming the oxide in the periodic
table. Metals tend to form basic oxides, non-metals tend to form acidic oxides, and metalloids tend to form
amphoteric oxides in their low oxidation states and acidic oxides in their higher oxidation states. For
example, As2O3 is amphoteric and As2O5 is acidic.
Many elements form several normal oxides in which the oxidation state of oxygen is −2 and that of the
element differs from one compound to another. The acidity of normal oxides tends to increase as the
oxidation state of the element increases and the compound becomes more covalent. This is illustrated for the
oxides of vanadium and lead in Table S3.A2.
Table S3.A2 The acid–base nature and bonding type of oxides of vanadium and lead
Compound VO V 2O 3 VO2 V2O5 PbO PbO2
Nature basic Basic amphoteric Amphoteric basic amphoteric
Bonding ionic largely ionic largely covalent Covalent ionic largely covalent
The structure and bonding type of oxides determine their properties. Like other ionic substances, ionic
oxides have high melting and boiling points, conduct electricity in the molten state, are hard and brittle, and
are more soluble in polar solvents (for example, water) than non-polar
solvents (for example, hexane). Covalent oxides (except boron(III)
oxide, B2O3, silicon (IV)oxide, SiO2) consist of discrete molecules so
weak London (dispersion) forces are the only intermolecular forces
present. Molecular covalent oxides tend to have low melting and
boiling points and hydrolyse with water.
The lower oxides of transition metals, where the transition metal is in
an oxidation state of +2 or +3, are ionic, and the higher oxides Figure S3.A3 Simple molecular
become increasingly covalent. Compare, for example, VO [V2+ O2-] structure for vanadium(V) oxide
and V2O5.
How can oxidation states be used to analyse redox reactions?

Oxidation states (or oxidation numbers, ONs) can be used to quickly check if a chemical reaction involves
electron transfer between species and is therefore a redox reaction. The oxidizing agent and reducing agent
can then be determined and the equation can be separated into oxidation and reduction half-equations.
Consider the equilibrium between yellow chromate(VI) ions, CrO42−, and orange dichromate ions(VI),
Cr2O72−, below:
2CrO42 −(aq) + 2H+ (aq) ⇋ Cr2O72−(aq) + H2O(l)
The oxidation number of chromium, ONCr, in CrO42− can be found as follows:
ONCr + (4 × ONO) = = −2
so ONCr + 4(−2) = −2
and ONCr = +6
Similarly the oxidation number of chromium, ONCr, in Cr2O72 − is:
(2 × ONCr) + (7 × ONO) = −2
(2 × ONCr) + 7(−2) = −2
(2 × ONCr) = +12
so ONCr = +6
The calculation clearly shows that the oxidation state of chromium has not changed in this equation (nor
have those of oxygen and hydrogen) so the reaction is not a redox reaction. It is, in fact, an acid–base
equilibrium involving proton transfer.
Consider the unbalanced equation below:
As2O3 (s) + KMnO4 (aq) + HCl (aq) → As2O5 (s) + MnCl2 (aq) + H2O (l)
The first thing to recognize is that K+ (aq) and Cl− (aq) are spectator ions in this reaction, and their removal
will simplify the analysis of the equation, which can be rewritten as follows:
As2O3 (s) + MnO4− (aq) + H+ (aq) → As2O5 (s) + Mn2+ (aq) + H2O (l)
ONs can now be applied to all species in the equation to identify the oxidant (oxidizing agent) and reductant
(reducing agent):
+3 −2 +7 −2 +1 +5 −2 +2 +1 −2
The ON of arsenic has increased from +3 to +5 (As2O3 has lost electrons and been oxidized, which is
additionally confirmed by the gain of oxygen) and the ON of manganese has decreased from +7 to +2
(MnO4− has gained electrons and been reduced, again confirmed by the loss of oxygen).
The equation can now be separated into two half-equations:
oxidation: As2O3 (s) → As2O5 (s)
reduction: MnO4− (aq) → Mn2+ (aq)
The half-equations can now be balanced as follows:
oxidation: As2O3 (s) + 2H2O (l) → As2O5 (s) + 4H+ (aq) + 4e−
reduction: MnO4− (aq) + 8H+ (aq) + 5e− → Mn2+ (aq) + 4H2O (l)
The equations are combined by cancelling the electrons. The least common multiple of 4 and 5 is 20, so the
oxidation half-equation is multiplied through by 5 and the reduction half-equation by 4. Water molecules,
hydrogen ions and electrons can then be cancelled to produce an overall balanced ionic equation:
oxidation: 5As2O3(s) + 10H2O(l) → 5As2O5(s) + 20H+(aq) + 20e−

reduction: 4MnO4− (aq) + 32H+(aq) + 20e− → 4Mn2+(aq) + 16H2O (l)
12 6
overall: 5As2O3(s) + 4MnO4−(aq) + 12H+(aq) → 5As2O5(s) + 4Mn2+(aq) + 6H2O(l)
The overall equation should be inspected to check that the number of atoms of each element is the same on
both sides and that the total charge (+8) is also the same on both sides.
The equation can also be balanced using the ONs directly, by following these steps:
1 Assign ONs to each atom and write them in above the equation.
+3 −2 +7 −2 +1 +5 −2 +2 +1 −2
2 Identify the oxidizing agent (oxidant) and reducing agent (reductant). As before, the ON of arsenic
has increased and that of manganese has decreased, so As2O3 is the reducing agent (reductant) and
MnO4- is the oxidizing agent (oxidant).
3 Draw a line to connect the atoms undergoing a change in ON and write in the change in ON. Note
that since two arsenic atoms have increased in ON from +3 to +5 that the total change = +4.
2 × (+2) = +4
+3 −2 +7 −2 +1 +5 −2 +2 +1 −2
−5
4 Insert coefficients to make the total increase in ON equal to the total decrease. It is then necessary to
balance the oxygen atoms by adding a coefficient in front of the water molecule, and to balance the
hydrogen atoms by adding a coefficient in front of the hydrogen ion. The final equation should be
carefully checked to ensure that the atoms and charges are correctly balanced on both sides.
+4 × 5 = +20
+3 −2 +7 −2 +1 +5 −2 +2 +1 −2
5As2O3 (s) + 4MnO4− (aq) + H+ (aq) → 5As2O5 (s) + 4Mn2+ (aq) + H2O (l)
−5 × 4 = −20
What are the arguments for and against including scandium as a

transition element?
Themes S2.3 The metallic model
A transition element is usually defined as an element which can produce a cation with a partially filled d
sublevel.
Other properties commonly ascribed to the transition elements are:
• formation of coloured compounds (due to d-d electronic transitions)
• formation of complexes and coordination compounds
• variable oxidation states
• paramagnetism (due to one or more unpaired d electrons)
• catalytic activity.
Scandium has the electron configuration 1s2 2s2 2p6 3s2 3p6 3d1 4s2. In the vast majority of its compounds,
scandium exists in a +3 oxidation state due to the loss of both its 4s electrons and its one 3d electron. These
compounds are white solids that (where soluble) produce colourless solutions. For these reasons, scandium
has not, historically, been considered to be a transition element.
However, in recent decades, a number of compounds of scandium in a +2 oxidation state have been
synthesized and characterized. One of the simplest of these is the ionic salt CsScCl3 [Cs+ Sc2+ 3Cl–] which is
blue-black in colour. Scandium also forms an anionic complex, Sc[N(NR2)3]–, where R = Si(CH3)3, with
scandium in oxidation state +2. These anions combine with potassium or caesium ions (which are themselves
complexed within large ring structures called cryptands or crown ethers) to form dark purple salts.
It should be noted that the rules for categorizing chemical elements and compounds are not always clear-cut,
and that exceptions to the rules often exist. Whilst there are arguments for and against including scandium as
a transition element, we are on safer ground in excluding zinc from the list, as there are no known
compounds of zinc in a +3 (or higher) oxidation state.
What is the nature of the reaction between transition element ions and
ligands in forming complex ions?
Transition element cations are relatively small and have a high charge density (that is, they are polarizing).
They therefore attract ions and molecules known as ligands.
Ligands contain atoms of p-block elements (such as oxygen, nitrogen, and halogens) that are more
electronegative than the first-row transition metal. Ligands also have at least one lone pair of electrons for
donation. Common ligands include water molecules, cyanide ions and hydroxide ions.
Figure S3.A4 shows the imagined generalized interaction between a transition metal cation, M3+, and water
molecules (the ligands). The water molecules act as Lewis bases (electron pair donors) and the M3+ cations
act as Lewis acids (electron pair acceptors). Coordination bonds are formed using empty orbitals in the
cation and an octahedral hexaaqua complex ion is formed. The coordination bonds are polar covalent and, in
a simple model which views the metal atom as approximately neutral, the charge is spread to the outside of
the ion, so that the final structure is a blending of the two structures in the middle of Figure S3.A4.
Figure S3.A4 The formation of a hexaaqua complex ion (involving M3+) where arrows represent coordination bonds
How can colorimetry or spectrophotometry be used to calculate the

concentration of a solution of coloured ions?
Inquiry processes Inquiry process 2 Collecting and processing data
For dilute solutions, the amount of light absorbed at a specific wavelength is directly proportional to the
concentration of the solution.
This relationship is called Beer's Law:
A = εlc
where A is the absorbance, ε = the molar absorptivity coefficient which takes into account the specific
properties of the molecules or ions which are absorbing light, l = sample solution path length in cm, and
c = molar concentration of solution.
A Beer’s Law plot is a calibration curve of absorbance plotted as a function of concentration. An absorption
spectrum must be acquired first to determine the wavelength of maximum absorbance (λmax) for the
compound being studied. To construct the plot, the absorbances of at least five solutions of known molar
concentrations (similar to the concentration expected in the unknown) are measured. A graph of absorbance
versus molar concentration is constructed and a best fit straight line is drawn through the data points (Figure
S3.A5).
The plot can be used in two ways to determine an
unknown concentration. The first way is graphical
interpolation: a horizontal line is drawn from the
value of the experimentally found absorbance on
the y-axis to the calibration curve and a vertical
line is then drawn to the x-axis to determine the
value of the unknown solution concentration.
The second way is mathematical: determine the
equation of the calibration line using data logging
software or a spreadsheet such as Excel. The
equation should take the form y = mx + c, where m
is the gradient and c is here the y-axis intercept, so
it can be rearranged to give
x = (y − c) / m
The concentration, x, can be determined by
Figure S3.A5 A graph of absorbance versus
substituting for y using the measured absorbance.
concentration (Beer’s Law calibration curve)
S3.2 Functional groups
What is unique about carbon that enables it to form more compounds

than the sum of all the other elements’ compounds?
There are three special features of covalent bonding involving carbon:
• Carbon atoms can bond to each other covalently to form long chains, and atoms of other elements
can then bond to the chain. Chains of carbon atoms can be ‘straight’ or branched.
• The carbon atoms in a chain can be bonded by single, double or triple covalent carbon–carbon bonds.
• Carbon atoms can also form cyclic (ring) compounds involving both single and multiple bonds.
Atoms of other elements have this property to a limited extent. For example, silicon atoms can form short
reactive chains such as Si3H6, and sulfur atoms can also form cyclic structures such as S8.
Carbon atoms are relatively small and the overlap with the orbitals of other atoms is effective, leading to
short, and hence strong, bonds.
Table S3.A3 X−X bond strengths for
Carbon not only forms multiple bonds with itself, but it can also group 14 elements
form strong double and triple covalent bonds with atoms of other
elements such as oxygen (the carbonyl functional group, >C=O) Bond Average bond
and with nitrogen (in nitriles, which contain the >C≡N group). enthalpy / kJ mol−1
C–C 346
The C–C bond is particularly strong compared to similar bonds
Si–Si 226
between other group 14 elements (Table S3.A3). This contributes
Ge–Ge 188
to the kinetic and thermodynamic stability of organic compounds.
The lack of bond polarity, the absence of lone pairs (non-bonded Sn–Sn 151
pairs of electrons) on carbon atoms and the lack of empty orbitals all contribute to a high activation energy
barrier to reaction.
The C−H bond is also significantly more stable than comparable bonds such as the Si−H bond (bond
enthalpies: C−H = 412 kJ mol−1; Si−H = 318 kJ mol−1).
Most hydrocarbons have exothermic standard enthalpies of formation, which implies that the molecules are
lower in enthalpy than their elements.
The reactions of most organic compounds with oxygen are exothermic so they are not thermodynamically
stable in the presence of oxygen. However, under standard conditions, the reactions with oxygen are
extremely slow due to large activation energies so organic compounds are kinetically stable. By contrast,
chain molecules based on silicon and hydrogen (known as silanes) react immediately on exposure to air, as
do the hydrides of the other group 14 elements.
What are the advantages and disadvantages of different depictions of

an organic compound (structural formula, stereochemical formula,
skeletal formula, 3D models, etc.)?
The advantage of a structural formula is that it shows the connectivity – the bonding between the atoms in
the molecule. One obvious disadvantage is that the molecular shape is not shown.
The advantage of a skeletal formula is that it simplifies large structures and highlights important atoms,
bonds, and functional groups. However, atoms can sometimes be forgotten in structures.
A stereochemical formula attempts to show the
tetrahedral arrangement of atoms or groups of
atom around a single chiral carbon atom. They
become less useful with complex molecules
that have two or more chiral centres.
There are three common types of physical or Figure S3.A6 Ball-and-stick, framework and space-filling
computer-generated molecular model, shown in models of the ethanol molecule, CH3–CH2–O–H
Figure S3.A6
• Ball-and-stick models show both the atoms (the balls) and the bonds (as sticks). Different colours are
used to identify different atoms so a key is required.
• Framework models show only the bonds. This emphasizes the arrangement of bonds within a
molecule but ignores the sizes of the atoms.
• Space-filling models show the relative size of each atom based on its van der Waals radius. (The van
der Waals radius is half of the distance of closest approach between two non-bonded atoms of an
element in a crystalline solid.) It does not show the bonds and it emphasizes the volume occupied by
each atom in the molecule.
How useful are 3D models (real or virtual) to visualize the invisible?

Tools Tool 2: Applying technology to collect data
Science models the physical world in order to understand and explain phenomena. A model can be viewed as
a connection between abstract theory and experiments.
Scientists use models to define, simplify and
clarify abstract concepts, as well as to develop
and explain theories and phenomena. An
important use of scientific models in science is
their contribution to visualization of complex
ideas, processes and systems. Interpretation of
symbols, understanding the particulate nature of
matter, and visualizing three-dimensional
structures are essential skills for solving problems
in chemistry.
Three-dimensional structures are important
because they can have significant effects on the
properties of molecules. Physical and computer-
generated three-dimensional models of molecules
are most important in organic chemistry due to
isomerism and the steric requirements of many Figure S3.A7 A computer-generated model of Taxol, a
organic reactions. natural anti-cancer drug from the Pacific yew tree
The three-dimensional shape of drug molecules is
a very important issue in drug design. The activity of a drug depends mainly on its interaction with
biological targets such as proteins inside or on cells (receptors, enzymes), nucleic acids (DNA and RNA) and
membranes (phospholipids and glycolipids). All these have complex three-dimensional structures which are
capable of interacting (binding) to each other in only one of the many possible arrangements in three-
dimensional space. It is the three-dimensional structure of the drug target that determines which of the
potential candidate drug molecules is bound within its cavity and with what affinity (strength).
The shape is a key factor in drug–receptor interaction so modern drug development often involves computer
modelling of candidate molecules and the biological molecules they interact with.
What is the nature of the reaction that occurs when two amino acids
form a dipeptide?
Proteins are linear condensation polymers formed by linking the carboxyl group of one amino acid to the
amino group of another amino acid. This type of linkage is called a peptide bond or an amide bond.
The formation of a dipeptide from two amino acids is a condensation reaction accompanied by the loss of
water molecules. A tripeptide is formed when three amino acids react in a condensation reaction and three
water molecules are eliminated (Figure S3.A8).
Under most conditions, the equilibrium position
of this reaction lies on the side of the reactants
rather than products. Hence, the biosynthesis of
peptide bonds requires an input of free energy
(from ATP). However, peptide bonds are quite
stable kinetically because the rate of hydrolysis
is extremely slow under physiological
conditions.
As a consequence of the peptide linkage, the
protein backbone exhibits directionality: all the
amino groups are located on the same side of the
carbon atoms. Thus, one end of a protein has a
free (unlinked) amino group (the N-terminus)
and the other end has a free carboxyl group (the
Figure S3.A8 Formation of a tripeptide
C-terminus).
The sequence of a protein chain is conventionally written with its N-terminal amino acid on the left and its
C-terminal amino acid on the right.
How can functional group reactivity be used to determine a reaction

pathway between compounds; for example, converting ethene into
ethanoic acid?
R3.4 Electron pair sharing reactions
Nature of Science Patterns and trends
In organic chemistry, a functional group is a specific atom or group of bonded atoms within a molecule that
is responsible for the characteristic chemical reactions of that compound. The same functional group will
behave in a similar way, undergoing similar reactions, regardless of the compound in which it is present. For
example, ethene, propene and cyclohexene will all react with bromine to form an addition product. The
bromine molecule will undergo addition across the alkenyl functional group to form a dibromoalkane.
The synthesis of an organic compound starts from a readily available starting material and proceeds via a
series of discrete chemical reactions (steps) known as a reaction pathway or synthetic route. Figure S3.A9
shows a selected number of functional group interconversions: the chemical conversions of one functional
group into another.
Figure S3.A9 Selected organic reaction pathways involving functional group interconversions:
M1 = free radical substitution; M2 = electrophilic addition and M3 = nucleophilic substitution
Functional group interconversions are the basis for the laboratory synthesis of ethanoic acid from ethene.
1 Ethene is converted to bromoethane in an addition reaction (alkane to halogenoalkane).
2 Substitution using sodium hydroxide converts this to ethanol (halogenoalkane to alcohol).
3 The ethanol is oxidized to ethanoic acid (alcohol to carboxylic acid).
This three-step synthesis involves functional group conversions without the need to shorten or lengthen the
carbon chain.
The laboratory synthesis of an organic compound may differ from that used in the chemical industry
because:
• In the laboratory it is difficult to obtain very high temperatures and pressures. For example, ethene
can be converted to ethanol in one step by passing steam and ethene over a catalyst of phosphoric(V)
acid and silicon dioxide at 300 °C and a pressure of 70 atmospheres (7092 kPa).
• Costs of raw materials and solvents are much more important in an industrial process.
• The use of very toxic reactants, such as cyanides (used to lengthen the carbon chain), should ideally
be avoided in industrial processes, but it might be acceptable to use small quantities under careful
control in the laboratory.
• The energy balance of an industrial process is important: heat released can be used elsewhere in the
plant, reducing costs. This is not an issue in laboratory preparations.
• It is helpful to eliminate purification procedures in large-scale manufacturing.
What is the influence of the carbon chain length, branching and the
nature of the functional groups on intermolecular forces?
London (dispersion) forces are the only intermolecular attractive forces that exist between non-polar
molecules such as alkanes, alkenes and arenes. In polar molecules, there are also dipole–dipole interactions
(in, for example, ketones, halogenoalkanes, ethers, esters and aldehydes) and/or hydrogen bonds (in amines,
amides, alcohols and carboxylic acids) to consider.
The relative boiling points of selected molecules can indicate the relative importance of various
intermolecular forces and the structural features that influence them. For example, consider three compounds
similar in size and shape: the alkane propane, the alcohol ethanol, and the halogenoalkane fluoroethane
(Table S3.A4).
Table S3.A4 Formulas and boiling points of propane, ethanol and fluoroethane
Formula CH3CH2CH3 CH3CH2OH CH3CH2F

Name Propane ethanol fluoroethane
Boiling point / °C −42 78 −32
Both the polar compounds, ethanol and fluoroethane, have higher boiling points than the non-polar propane.
This is explained by the combination of London forces and dipole–dipole attractive forces in the ethanol and
fluoroethane liquids that are absent in propane. The significantly higher boiling point of ethanol suggests that
the hydrogen bonds in ethanol must be unusually strong.
When comparing the boiling points of related compounds as a function of the alkyl group, we find that the
boiling point increases with the number of carbon atoms. For example, butane, propanol-1-ol and 1-
fluoropropane all have higher boiling points than propane, ethanol and fluoroethane due to the presence of a
longer alkyl group and hence more extensive or stronger dispersion forces (Table S3.A5).
Table S3.A5 Formulas and boiling points of butane, propan-1-ol and 1-fluoropropane
Formula CH3(CH2)2CH3 CH3(CH2)2OH CH3(CH2)2F

Name butane propan-1-ol 1-fluoropropane
Boiling point / °C −1 97 −2.5
With respect to the halogen in a group of halogenoalkanes, the boiling point increases down group 17;
fluoroalkanes have the lowest boiling points, iodoalkanes the highest. This trend matches the order of
increasing polarizability of the halogens. Polarizability is a measure of how much the electron distribution
around an atom is distorted by an electric field. It is a significant factor in determining the strength of
London (dispersion forces) and dipole-dipole forces.
The boiling points of the chlorinated derivatives of methane (Table S3.A6) increase with the number of
chlorine atoms because of an increase in the London forces.
Table S3.A6 Formulas and boiling points of chloromethanes
Formula CH3Cl CH2Cl2 CHCl3 CCl4

Name chloromethane dichloromethane trichloromethane tetrachloromethane
Boiling point / °C −24 40 61 77
Fluorine is unique among the halogens in that increasing the number of fluorine atoms does not produce a
trend of higher boiling points (Table S3.A7).
Table S3.A7 Formulas and boiling points of fluoroethanes
Formula CH3CH2F CH3CHF2 CH3CF3 CF3CF3

Name fluoroethane 1,1-difluoroethane 1,1,1-trifluoroethane Hexafluoroethane
Boiling point / °C −32 −25 −47 −78
The difluoro compound, CH3CHF2, boils at a higher temperature than CH3CH2F, but the trifluoro compound,
CH3CF3, boils at a lower temperature than either of them. The hexafluoro compound, CF3CF3, has the lowest
boiling of any of the fluorinated derivatives of ethane. The reason for this unexpected behaviour is the very
low polarizability of fluorine and a decrease in induced-dipole–induced-dipole forces that accompanies the
incorporation of fluorine atoms into a molecule.
The final factor that affects the strength of intermolecular forces is branching. This can be most clearly seen
in alkanes due to the absence of a functional group. The straight-chain octane molecule has a higher boiling
point than its branched isomer: octane boils at 126 °C, 2-methylheptane at 118 °C. Octane molecules have a
larger surface area and molecules can approach each other closely and experience stronger dispersion forces.
2-methylheptane molecules have a smaller surface area and cannot approach each other so closely due to the
presence of the bulky methyl group, hence the London forces are weaker and the boiling point is lower.
How does the fact that there are three isomers of dibromobenzene
support the current model of benzene’s structure?
The delocalized model of benzene, with all
carbon–carbon bonds equivalent in length and
strength, predicts three structural isomers of
dibromobenzene (Figure S3.A10). These are
positional isomers.
However, a localized (Kekulé) structure would Figure S3.A10 Structural isomers of dibromobenzene
give two 1,2 isomers of dibromobenzene (Figure
S3.A11). In one isomer, the two bromine atoms would be attached to
carbon atoms connected by a double bond and in the other isomer, the
bromine atoms should be attached to carbon atoms connected by a single
bond.
The delocalized model based on molecular orbital theory explains the Figure S3.A11 Hypothetical
observation that the bromination of bromobenzene gives three structural isomers of 1,2-
dibromobenzene, assuming a
dibromobenzene isomers rather than four.
localized structure for benzene
What features of a molecule determine whether it is IR active or not?

All molecules vibrate at temperatures above absolute zero. The energy associated with molecular vibration is
quantized, like the electron energies of atoms and molecules.
Not all vibrations of molecules will absorb infrared radiation. To absorb in the infrared, a molecule must
have a dipole arising from a polar bond, because this allows it to interact with the electromagnetic radiation.
Molecules such as carbon monoxide, CO, and hydrogen fluoride, HF, which have a bond dipole, absorb
infrared radiation but hydrogen, H2, oxygen, O2, and nitrogen, N2, do not because their non-polar bonds do
not give rise to dipoles.
To vibrate more energetically, a molecule must absorb a photon of a specific wavelength in the IR region.
However, only vibrations which cause the dipole moment of the molecule to change will absorb infrared
radiation.
Consider the symmetrical stretching vibrations of
the carbon dioxide molecule (CO2), which is linear,
and the sulfur dioxide molecule (SO2), which is V-
shaped/bent/angular (due to the presence of the
lone pair on the central sulfur atom).
The type of vibration – the symmetric stretch –
does not change the dipole moment of the carbon
dioxide molecule, since the effects of the two bond
dipoles cancel (as their values increase and then
decrease together) and so this vibration of the
carbon dioxide molecule does not absorb infrared Figure S3.A12 Symmetrical stretching vibrations of
radiation. carbon dioxide and sulfur dioxide molecules
However, in the case of the sulfur dioxide

molecule, the symmetrical stretching vibration does
change the dipole moment of the molecule because
the sulfur atom moves further away from the two
oxygen atoms and the two bond dipoles do not
cancel.
The asymmetrical stretching and bending vibrations
of the carbon dioxide molecule do absorb infrared as
the dipole moment of the molecule does change in
each case.
Figure S3.A13 Asymmetrical stretching and bending
vibrations of the carbon dioxide molecule
What properties of a greenhouse gas determine its ‘global warming

potential’?
Themes R1.3 Energy from fuels
The contribution of a greenhouse gas to the warming of the atmosphere depends on three factors:
• the abundance of the gas in the atmosphere
• the ability of the gas to absorb infrared radiation
• the lifetime of the gas molecules, that is, how long they remain in the atmosphere before being
removed by chemical processes.
The second and third factors are often combined to give a figure called the global warming potential (GWP).
Carbon dioxide is assigned a GWP of 1.
Some gases are extremely effective at absorbing infrared radiation but are quickly removed from the
atmosphere for a very short time, minimizing their contribution. Other gases are less effective absorbers of
infrared radiation but remain in the atmosphere for many years so their contribution to global warming is
more significant.
Water absorbs infrared over a broad range of frequencies. The GWP of water is sometimes given as 0.1 but
the overall contribution is often not calculated because water vapour is constantly cycling through the
atmosphere and its concentration varies according to temperature and location. Typically, the percentage of
water vapour in the lower atmosphere ranges from 1% to 4%: higher than that of any other greenhouse gas.
Estimates of water’s contribution to global warming range from 36% to 75% making it the most important
greenhouse gas. Increased atmospheric temperatures lead to more rapid evaporation of the oceans, and a
larger capacity of the air to carry water vapour. This leads to an increased concentration of water in the
atmosphere, which may lead to further warming.
The percentage of carbon dioxide in the atmosphere is only 0.042%, or about one-thirtieth that of water.
However, carbon dioxide is more efficient than water at absorbing infrared radiation (GWP = 1, by
definition) and it absorbs in a window of wavelengths at which water does not absorb. Increases in carbon
dioxide concentration therefore disturb the equilibrium of absorption and transmission though the
atmosphere.
THEME R
R1.1 Measuring enthalpy changes
What is the relationship between temperature and kinetic energy of

particles?
Themes S1.1 Introduction to the particulate nature of
matter
Absolute temperature (measured in kelvin) is a measure of the average kinetic energy of the particles in a
system. The kinetic energy of particles in a system is dependent on the speed at which the particles move.
Thus, the faster the particles in a system move, the higher the kinetic energy and the higher the temperature.
Consider one mole of helium gas at a temperature of 300 K. To a very good approximation the helium atoms
will behave ideally; that is, we can ignore intermolecular forces and assume that the atoms behave like point
particles.
The speed of the atoms in the system is given by the Maxwell-Boltzmann distribution. The particles have a
range of speeds. Because of the skewed shape of the distribution, the average speed lies slightly to the right
𝟏𝟏
of the most probable speed, and the speed of the particles which have kinetic energy equal to average
𝟐𝟐
kinetic energy of the sample (known as the root-mean-square speed) is even higher.
Because helium atoms do not form molecules, they do not undergo molecular vibrations or rotations and
therefore their energy is purely translational (the energy associated with movement through space). The
3
energy of one mole of helium atoms is equal to 𝑅𝑅𝑇𝑇, where R is the universal gas constant (8.31 J K−1 mol−1)
2
and T is the absolute temperature, in kelvin. Therefore:
3
KE(He) = 𝑅𝑅𝑅𝑅
2
3
= × 8.31 × 300
2
= 3739.5 J mol−1
= 6.21 × 10−21 J per He atom (after dividing by Avogadro’s number)
Using the relationship between kinetic energy (KE), speed (v) and the mass of a He atom (6.65 × 10−27 kg)
we can determine the root-mean-square speed of a helium atom.
1
KE(He) = 𝑚𝑚𝑣𝑣 2
2
K.E.
𝑣𝑣rms = � 1
𝑚𝑚
2
6.21×10−21
= �1×6.65×10−27
2
≈ 1370 m s−1 (3 s.f.)
Remember that the most probable speed of a He atom at this temperature will be somewhat less than this.
If the mole of helium gas was replaced with a mole of argon gas at the same temperature, the average speed
of the atoms would be lower, as argon atoms have a greater mass than helium.
Most combustion reactions are exothermic; how does the bonding in N2

explain the fact that its combustion is endothermic?
Combustion reactions are loosely defined as reactions involving oxygen which are usually accompanied by
the generation of heat and light, that is, a flame. For this reason, it might be assumed that combustion
reactions are always exothermic processes. However, the combustion of nitrogen gas in oxygen is
endothermic. When nitrogen undergoes combustion a range of different oxides can form, including NO,
NO2, N2O, N2O3, N2O4 and N2O5. The enthalpies of formation of these gases are listed in the table.
Oxide Equation ΔfH⦵ / kJ
mol−1
NO 1
N2(g)
1
+ 2O2(g) → +91.3
2
NO(g)
NO2 1
N2(g) + O2(g) → +33.2
2
NO2(g)
N2O 1
N2(g) + 2O2(g) → +82.1
N2O(g)
N2O3 3
N2(g) + 2 O2(g) → +91.2
N2O3(g)
N2O4 N2(g) + 2O2(g) → +9.2

N2O4(g)
Note that each equation representing the formation of a nitrogen oxide (NxOy) can also be regarded as an
equation representing the combustion of nitrogen with a variable number of moles of oxygen. Because each
of the enthalpies of formation is positive, the combustion of nitrogen is endothermic in every equation. This
is a consequence of the short, strong triple bond present in molecular nitrogen which has a correspondingly
large bond enthalpy of 945 kJ mol−1. You will see in the next section that:
Δr 𝐻𝐻 = Σ𝐸𝐸(bonds broken) − Σ𝐸𝐸(bonds formed)
In each equation in the table because of the high amount of energy required to break the N2 bond, the energy
required to break the bonds in the reactants (N2 and O2) exceeds the energy released when new bonds are
formed in the NxOy product, and hence the combustion (formation) equation is endothermic in every case.
What observations would you expect to make during an endothermic

and an exothermic reaction?
Tools Measuring variables
Inquiry Inquiry process 2: Collecting data
processes
In general, one or more of the following observations may be indicative that a chemical reaction is occurring:
• colour change
• production of an odour
• change of temperature
• evolution of a gas
• formation of a solid precipitate
• production of light and/or sound
• a substance is burning and undergoing combustion.
The key observation that tells you that a reaction is exothermic is a transfer of heat to the surroundings
(consider the warmth felt around a Bunsen burner flame, or the increase in temperature of a solvent in an
aqueous reaction). Conversely, the reaction vessel in which an endothermic reaction occurs (for example,
between solid sodium hydrogen carbonate and aqueous citric acid) will feel cool to the touch as heat is
removed from the tips of your fingers.
When a small piece of magnesium is placed in dilute hydrochloric acid in a test tube, a vigorous reaction
occurs summarized by the following equations.
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
or
Mg(s) + 2H+(aq) → Mg2+(aq) + H2(g)
Heat energy transferred from the reaction to the surroundings causes a rise in the temperature of the reaction
mixture, test tube, and air surrounding the test tube. This is a clear indication that chemical potential energy
is lost by the reactants and is transferred to the surroundings; an exothermic reaction has occurred.
Why do calorimetry experiments typically result in a smaller change in

temperature than is expected from theoretical values?
Tools Tool 1: Applying techniques: Calorimetry
Inquiry Inquiry process 3: Evaluating
processes
The temperature change in calorimetry experiments is typically lower than expected from theoretical
enthalpy change values. This is due to three main problems associated with the use of calorimeters:
• The desired reaction does not (fully) occur. This is relevant to enthalpies of combustion where
incomplete combustion, a side reaction, occurs.
• Loss of heat to the surroundings (exothermic reactions) or absorption of heat from the surroundings
(endothermic reactions). This unwanted flow of heat can be reduced by ensuring the calorimeter is
well insulated by, for example, lagging it.
• Using an incorrect heat capacity in the calculation of the heat transferred. For example, if a copper
can is used as a calorimeter during an enthalpy change of combustion investigation:
• heat transferred = [mass of water × specific heat capacity of water × temperature change] +
[mass of copper × specific heat capacity of copper × temperature change]
How can the enthalpy change for combustion reactions, such as for
alcohols or food, be investigated experimentally?
Tools Tool 1: Applying techniques
Inquiry
Inquiry process 1: Designing and controlling
processes
variables
Inquiry process 2: Collecting and processing data
Inquiry process 3: Concluding and evaluating
One function of food following digestion is to supply us with energy. The nutrients (products of the digestion
of food) are oxidized slowly and completely inside cells to form carbon dioxide and water, and useful energy
is transferred. This enzyme-controlled process is known as aerobic respiration.
The energy we need in depends on our body size, the climate and the level of physical activity. For example,
a person lying down needs around 7500 kJ per day and a person doing manual work 15 000 kJ per day.
The enthalpy change of combustion of a dried sample of food can be investigated using calorimetry.
Calorimeters range from very rudimentary copper cans to much more sophisticated bomb calorimeters. The
operator measures the heat change of the calorimeter, and providing its heat capacity, C, is known, the
amount of heat energy released by the reaction can be determined.
The foods that supply energy are carbohydrates (starches and sugars), lipids (fats and oils) and proteins.
Carbohydrates supply around 17 kJ g−1; fats, 37 kJ g−1; and proteins, 17 kJ g−1. These are approximate figures
because all are mixtures of variable composition.
R1.2 Energy cycles in reactions
How would you expect bond enthalpy data to relate to bond length and
polarity?
Effect of bond length

Bond length is defined as the distance between the nuclei of two bonded atoms. The larger the atoms joined
by a particular covalent bond, the longer the covalent bond length. This trend is demonstrated by the bond
lengths in group 17 elements.
Bond length / 10−12 m Bond enthalpy / kJ
mol−1)
F–F 142 159
Cl–Cl 199 242
Br–Br 228 193
I–I 267 151
Bond length and bond enthalpy correlate well. Bond enthalpy decreases as bond length increases. The data
shows that the bond energy of I–I is lower than that of Br–Br. Fluorine, however, does not follow this trend
and has a surprisingly low bond enthalpy, despite the F–F bond being very short. This is accounted for by
lone pair–lone pair repulsion of the non-bonding electrons on the two very close F atoms.
The correlation between bond length and bond strength is most likely to be observed when comparing non-
polar bonds between similar elements where the orbital overlap effects are similar.
Effect of number of bonding electrons
The more pairs of bonding electrons present in a covalent bond, the greater the strength of the bond.
This is because an increasing number of bonding pairs of electrons between the nuclei leads to an increase in
electrostatic forces of attraction and consequently the nuclei are pulled closer together.
Hence, we expect triple bonds to be stronger than double bonds, and these to be stronger than single. This is
shown clearly in the chart below which plots the length and strength of different carbon to carbon bonds.
Carbon–carbon Bond enthalpy / kJ Bond length / 10−12
bond mol −1
m
single 346 154
double 614 134
triple 839 120
Effect of bond polarity

Bonds become more polar as the difference in electronegativity between the two bonded atoms increases.
This increase in polar or ionic character reinforces the covalent bond. Reinforcement of a covalent bond by
its ionic character was proposed by Linus Pauling in the work which led to his scale of electronegativity.
A–B bonds are usually stronger than the average of the A–A and B–B bonds. This means that the A–B bond
enthalpy is greater than the average of the A–A and B–B bond enthalpies. This is due to the presence of ionic
contributions to the covalent bond.
For example, the H–F bond enthalpy (567 kJ mol−1) is much greater than the average of the H–H and F–F
bond enthalpies (297.5 kJ mol−1). However, the H–I bond enthalpy (298 kJ mol−1) is only slightly more than
the average of the H–H and I–I bond enthalpies (293.5 kJ mol−1). Hydrogen fluoride has the greater tendency
towards ionic bonding [H+F−] and hydrogen iodide has a smaller tendency towards ionic bonding. As the
ionic character increases, the bond becomes increasingly stronger than would be expected.
How does the strength of a carbon–halogen bond affect the rate of a

nucleophilic substitution reaction?
The reactivity of a halogenoalkane (R–Hal) depends on the identity of the halogen atom and the structure of
the molecule.
There are two opposing factors that affect the rate of nucleophilic substitution:
1 The polarity of the C–Hal bond. Electronegativity decreases on going down the group from chlorine to
iodine. This suggests that 1-chlorobutane should react fastest with nucleophiles because it contains the
most electron-deficient carbon atom.
2 The C–Hal bond enthalpy. For substitution to occur, the C–Hal bond must be broken and this is
facilitated if the bond is weak (low bond enthalpy). This implies that the 1-iodobutane should react
fastest because it has the weakest C–Hal bond (see table).
Bond C–F C–Cl C-Br C-I
Enthlpy /kJ 285 228
492 324
mol−1
Experiment shows that 1-iodobutane is hydrolysed the most rapidly, so the effect of bond strength appears to
outweigh that of polarity.
Reactivity of the halogenoalkanes appears to correlate relatively well with the energy of the C–Hal bond
being broken. It is, perhaps, an important term in determining the activation energy.
However, the use of bond enthalpies should be viewed as a ‘rule of thumb’ and not the only contributing
factor in determining the relative reactivity of different halogenoalkanes. Other factors, such as the identity
of the carbon backbone and the solvent used in a reaction, can significantly affect the rate of a substitution
reaction.
Would you expect allotropes of an element, such as diamond and

graphite, to have different ΔHf⦵ values?
Enthalpy of formation, ∆𝐻𝐻𝑓𝑓 ⦵, is defined as the enthalpy change when one mole of a substance in the
standard state (1 bar pressure, i.e. 105 kPa and 298 K) is formed from its pure elements under the same
conditions.
Allotropes are defined as the different physical forms in which a pure element can exist. When the standard
form of an element is converted to an allotropic form (under standard conditions), the enthalpy change which
occurs is by definition equal to the enthalpy of formation of the allotrope. For example:
C(s, graphite) → C(s, diamond) ∆𝐻𝐻𝑓𝑓 ⦵ = +1.90 kJ mol−1
60C(s, graphite) → C60(s) ∆𝐻𝐻𝑓𝑓 ⦵ = +2300 kJ mol−1
3
O2(g) → O3(g) ∆𝐻𝐻𝑓𝑓 ⦵ = +142.7 kJ mol−1
2
S(s, rhombic) → S(s, monoclinic) ∆𝐻𝐻𝑓𝑓 ⦵ = +0.3 kJ mol−1
Consider the conversion of graphite to diamond. This can be viewed with the bonding of the two different
structures in mind. To complete this transition, all the bonds in the graphite structure must be broken and the
new bonds in the diamond formed. In both cases we know that strong covalent bonds exist between the
carbon atoms in the structure (see Chapter S2.2, page 149 for more detail on the structure of the two
allotropes). However, only if the energy input and output from breaking the graphite structure and forming
the diamond structure are equal, would the enthalpy of formation of the two allotropes be equal.
What are the factors that influence the strength of lattice enthalpy in an
ionic compound?
The lattice enthalpy of an ionic crystal can be expressed in a general formula:

MaXb(s) → aMb+(g) + bXa−(g)
For example, the lattice enthalpy of lithium fluoride is the enthalpy change for the reaction:
LiF(s) → Li+(g) + F−(g) ΔHL⦵ = +1049 kJ mol−1
The size of the lattice enthalpy is controlled by the charges on the ions, their ionic radii and the packing
arrangement of the ions (type of lattice). According to Coulomb’s law, the attractive force operating between
two adjacent oppositely charged ions in contact can be expressed as follows:
charge on positive ion × charge on negative ion
force ∝
𝑑𝑑 2
where d represents the distance between the nuclei of the two ions.
Two highly charged and small ions in contact with one another will have a stronger force of attraction to one
another than two ions with a low charge and large distance separating their nuclei.
The effect ionic radius has can be seen in the alkali metal fluorides (Table R1.A5). As the alkali metal ion
gets larger (down the group), the lattice enthalpy decreases.
Table R1.A5. Lattice enthalpies of alkali metal fluorides.
Allotrope of phosphorus Enthalpy of formation / kJ mol−1
Alkali metal fluoride ΔHL⦵

LiF 1049
NaF 930
KF 829
RbF 795
CsF 759
The lattice enthalpy of magnesium oxide, MgO, is about four times greater than the lattice enthalpy of
sodium fluoride, NaF.
ΔHL⦵[MgO(s)] = +3889 kJ mol−1
ΔHL⦵[NaF(s)] = +902 kJ mol−1
This is largely due to the doubling of the charges of the ions. The sum of ionic radii and the lattice structures
of magnesium oxide and sodium fluoride are similar.
R1.3 Energy from fuels
Which species are the oxidizing and reducing agents in a combustion

reaction?
Combustion reactions occur when a fuel reacts with oxygen. Reactive metals, non-metals, and organic
compounds are able to act as fuels. The complete combustion of hexene is represented by the equation:
C6H12(s) + 9O2(g) → 6CO2(g) + 6H2O(l)
Consider the average oxidation number of each atom in the compounds (Table R1.A6).
Table R1.A6 Oxidation numbers of elements in the
combustion reaction of hexene
Oxidation number
Element Reactants Products
carbon −2 +4
oxygen 0 −2
hydrogen +1 +1
The carbon in hexene is oxidized (its oxidation number increases) and it, therefore, is the reducing agent.
Molecular oxygen is reduced (its oxidation number decreases) and it, therefore, is the oxidizing agent.
This can be extended to all combustion reactions. The fuel is the reducing agent and molecular oxygen is the
oxidizing agent.
If incomplete combustion occurs, carbon is not oxidized up to its maximum oxidation state (+4), however,
oxygen is still the oxidizing agent.
What might be observed when a fuel such as methane is burned in a

limited supply of oxygen?
Inquiry Inquiry process 2: Collecting and processing data
processes
When a well-mixed mixture of methane and excess oxygen is burnt, carbon dioxide and water are produced.
The flame is light blue. If a limited supply of oxygen is available when methane is burnt, incomplete
combustion occurs. The flame appears orange because the hot solid products of incomplete combustion
incandesce.
The unburnt carbon, along with partially oxidized solid products, are referred to as soot. The soot is a black
dust which can be deposited on surfaces. If a glass beaker is placed above a fuel undergoing incomplete
combustion the glass will quickly show the soot being deposited on it. Fuels which have a tendency to
undergo incomplete combustion are referred to as having ‘smokier’ flames because a lot of partially oxidized
particles which contribute to soot are produced.
Soot produced by incomplete combustion occurring in cars and industrial processes builds up on surfaces
exposed to the atmosphere. The photograph shows a building, half of which has been cleaned. You can
clearly see the deposited soot on the left hand building.
Why do larger hydrocarbons have a greater tendency to undergo

incomplete combustion?
Hydrocarbons must first be vaporized or broken down into gaseous species (in a process called pyrolysis)
before they can react with surrounding oxygen. Complete combustion needs good mixing of the fuel with
excess oxygen which is possible only if the fuel is gaseous or volatile under standard conditions. For larger
hydrocarbons, good mixing with oxygen is even more important because they require a greater amount of
oxygen to combust completely. Because larger hydrocarbons are not as volatile as shorter-chain ones, larger
hydrocarbons are less likely to be converted to the gaseous state and hence well mixed with an excess of
oxygen. The result is that larger hydrocarbons have a greater tendency to undergo incomplete combustion
because the oxygen demand required for complete combustion cannot be fulfilled by oxygen surrounding the
burning fuel.
One way to encourage complete combustion is to ensure high airflow over the fuel. Solid-fuel fires burn
much better with the help of wind, and for the same reason, you blow over a stuttering fire in an effort to
keep it burning.
How does limiting the supply of oxygen in combustion affect the

products and increase health risks?
Themes R2.1 How much? The amount of chemical
change
When hydrocarbons are burnt in a limited supply of oxygen, carbon and partially oxidized carbon
compounds are produced. These products include particulates and carbon monoxide, CO, and both are a risk
to our health.
The particulates are mainly the unburnt products of pyrolysis on the fuel. The size of the particulates vary,
but most of the particulates produced fall in the PM2.5 range. This means they have a diameter of 2.5 × 10−6
m or less. These particulates can travel deep into our lungs, and the effect they have is especially harmful for
the very young or old, and those with heart or lung diseases. Particulates have also been linked with lung
cancer and asthma.
Carbon monoxide is a poisonous gas which poses severe and immediate health risks. Carbon monoxide binds
strongly with haemoglobin and reduces the ability of our blood to transport oxygen to the cells in our body.
Inhalation of carbon monoxide can quickly lead to death because our body becomes starved of oxygen.
Open fires, and particularly those indoors where the supply of oxygen may be limited and the products can
more readily accumulate, are discouraged because of the health risk the combustion products pose.
Why is a high activation energy often considered to be a useful property

of a fuel?
Fuels are thermodynamically unstable in relation to their combustion products. This is why they release
useful energy when combusted.
The high activation energy to combustion that many fuels have makes them kinetically stable under standard
conditions. This is incredibly useful because it means that fuels can be transported and stored relatively
safely without them reacting. Petrol, for example, can be stored in a metal tank until it is needed for use in
automobiles. Only when the petrol is provided with enough energy in the hot engine (from an electrical
spark) will it be oxidized and release the chemical potential energy it stores.
Why is carbon dioxide described as a greenhouse gas? (HL only)

Themes S3.2 The covalent bond
A greenhouse gas has the effect of heating the Earth’s atmosphere because it can absorb and emit infrared
radiation. A molecule can do this only if it has an dipole. Nitrogen and oxygen, being diatomic molecules, do
not have permanent dipoles, and create no temporary dipoles when they vibrate. They are not able to absorb
IR radiation and are not greenhouses gases. Water and carbon dioxide do absorb and emit IR radiation and,
therefore, are greenhouses gases.
Inspection of the carbon dioxide molecule suggests that it has no permanent dipole: the individual C=O bond
dipoles cancel out, as the molecule is linear.
However, one of the vibrational modes of carbon dioxide is a so-called asymmetrical stretching mode, in
which the symmetry of the molecule is disrupted and a temporary dipole formed. Vibrational transitions of
carbon dioxide can therefore occur, resulting in emission or absorption in the infrared at a wavenumber of
2360 cm−1. Carbon dioxide also has a second vibrational mode corresponding to a bending vibration. This
mode absorbs much more weakly at a wavenumber of 670 cm−1.
What are some of the environmental, economic, ethical and social

implications of burning fossil fuels?
Nature of science The global impact of science
• Fossil fuels are finite resources which humans exploit to meet our energy needs. Some of the
implications of the mass extraction and combustion of fossil fuels are:
• Damage to the Earth’s crust. When fossil fuels are extracted from the Earth’s crust it can leave
unsightly scars, for example, mining pits. Activities such as fracking can cause disturbance to the
crust and potential earthquakes and land slips.
• Damage to ecosystems. Removing fossil fuels causes damage to the local landscape which disrupts
the ecosystem.
• Production of greenhouse gases. Combustion of fossil fuels produces lots of carbon dioxide. Carbon
dioxide is a greenhouse gas and is contributing to anthropogenic climate change. Is it fair to pass this
problem to future generations?
• Contribution to acid deposition. Sulfur impurities in fossil fuels lead to acid deposition.
• Reduction in air quality. Burning fossil fuels leads to particulates and smog. This can have a big
effect on people’s life expectancy and quality of life, especially in poorer areas of the world.
• Ocean acidification. Oceans are becoming more acidic as the levels of carbon dioxide in the
atmosphere rise. This could have unknown effects on ecosystems and biodiversity and cause
runaway climate change.
• Concentration of wealth in hydrocarbon rich areas. Some countries have vast supplies of fossil fuels,
others have very little.
• Climate refugees. The effects of climate change, such as rising water levels and warmer
temperatures, are causing areas of the world to become uninhabitable. This is predicted to get much
worse in the future. Developed economies have burnt vast amounts of fossil fuels to drive economic
growth, but the impacts of climate change most often fall on countries which have not benefitted in
the same way from the burning of fossil fuels.
• Cost of climate change mitigation. There is an urgent need to reduce usage of fossil fuels, and to
capture the carbon dioxide released when they are burnt. This will be a costly endeavour that needs
to be financed by those who have benefited from the use of fossil fuels, and who can afford to lead
the way in reducing emissions.
What are the main differences between a fuel cell and a primary (voltaic)
cell?
Primary cells are single-use electrochemical cells which create a potential difference between the two
electrodes. Primary cells will operate until the reactants at either electrode have been exhausted, when this
point is reached the cell will no longer be able to produce a potential difference.
In a zinc and copper based primary cell (Daniell cell), the reactants are the zinc strip (anode) and the aqueous
copper(II) ions.
The half-equations for the reactions occurring are:

Zn(s) → Zn2+(aq) + 2e−
Cu2+ + 2e− → Cu(s)
Fuel cells have a continuous supply of reactants from which to produce a steady electric current. They use a
variety of fuels including hydrogen, hydrocarbons (such as methane) and alcohols. Inside a fuel cell, energy
from the redox reaction between a fuel and oxygen is used to create a potential difference (voltage). As long
as the fuel and oxidant are continually supplied to the cell, it will continue to create a potential difference.
R1.4 Entropy and spontaneity (HL only)
Why is the entropy of a perfect crystal at 0 K predicted to be zero?

matter
Entropy measures the dispersal of energy within a chemical system: that is, the number of microstates or
distinguishable ways (W) that energy can be distributed amongst the particles the system and their different
types of motion (translational, vibrational and rotational).
In (classical) theory, at 0 K all molecular motion has ceased, so a perfect crystal has one microstate: there is
only one way of arranging the particles into the perfect crystal, and there are zero quanta of energy that can
be distributed between the atoms in the crystal.
Substituting W = 1 into the Boltzmann formula, 𝑆𝑆 = 𝑘𝑘 ln 𝑊𝑊, gives S = 0, so we predict that the entropy of a
perfect crystal is zero at 0 K.
However, in the real world, it is impossible to create a perfect crystal. Also, due to the Heisenberg
uncertainty principle, the energy of any real system fluctuates meaning it has a finite minimum energy
(called zero-point energy). Therefore, reaching absolute zero in temperature (0 K) is physically impossible
and the entropy of a system approaches a constant value when its temperature approaches absolute zero.
What is the likely composition of an equilibrium mixture when ∆G⦵ is

positive?
Themes R2.3 How far? The extent of chemical
change
An equilibrium mixture will move towards a minimum in Gibbs free energy, G. As an equilibrium reaction
proceeds from pure reactants towards products, the Gibbs energy of the mixture decreases, reaching a
minimum when equilibrium is reached.
If the ∆𝐺𝐺 ⦵ of a reaction is positive, the minimum in Gibbs free energy will lie towards the reactants. If ∆𝐺𝐺 ⦵
is very large and positive, the minimum in Gibbs free energy will lie very close to the reactant side. For
example, if ∆𝐺𝐺 ⦵ is +23 kJ mol−1, the equilibrium is reached with less than 0.01% of products. However,
when the ∆𝐺𝐺 ⦵ is a smaller positive value, the equilibrium mixture will contain an observable amount of
both reactants and products.
The equation which links the equilibrium constant, K, to ∆𝐺𝐺 ⦵ is:
𝑅𝑅𝑅𝑅
∆𝐺𝐺 ⦵ = − 𝐾𝐾
ln
Rearranging this to make K the subject:
−∆𝐺𝐺 ⦵
𝐾𝐾 = 𝑒𝑒 𝑅𝑅𝑅𝑅
This shows K, when plotted against ∆𝐺𝐺 ⦵ , will take the form y =𝑒𝑒 −𝑥𝑥 .
A positive value for ∆𝐺𝐺 ⦵ gives an equilibrium constant, K < 1.
Values of K < 1 indicate that a process favours the reactants and that the equilibrium mixture will contain
only a very small amount of products.
How can electrochemical data also be used to predict the spontaneity of

a reaction?
The second law of thermodynamics tells us that processes which increase the total entropy of the universe
are spontaneous. From this law it follows that any process with a decrease in Gibbs (free) energy will be
spontaneous.
ΔG < 0 spontaneous
Gibbs energy is linked to the standard cell potential, 𝐸𝐸 ⦵ cell , by the following equation:
∆𝐺𝐺 ⦵ = −𝑛𝑛𝑛𝑛𝐸𝐸 ⦵ cell
where
n = amount of electrons transferred (in moles) in the cell equation
F = Faraday constant (96 500 C mol−1)
The equation shows that any reaction with a positive cell potential will have a negative ΔG and therefore be
spontaneous.
𝐸𝐸 ⦵ cell > 0 spontaneous
To determine whether a reaction is spontaneous or not, its standard cell potential can be calculated.
To calculate the standard cell potential of a reaction the two relevant standard reduction potentials are used:
𝐸𝐸 ⦵ cell = 𝐸𝐸 ⦵ red − 𝐸𝐸 ⦵ ox
where
𝐸𝐸 ⦵ red = reduction potential of half equation undergoing reduction
𝐸𝐸 ⦵ ox = reduction potential of half equation undergoing oxidation
For example, the reaction between copper and silver(I) ions:
Cu(s) + 2Ag+(aq) → Cu2+ + 2Ag(s)
The relevant standard reduction potentials

Ag+(aq) + e− → Ag(s) 𝐸𝐸 ⦵ = +0.80 V
Cu2+(aq) + 2e- → Cu(s) 𝐸𝐸 ⦵ = +0.15 V
𝐸𝐸 ⦵ cell = 0.80 V – 0.15 V = 0.65 V The reaction is spontaneous.

When copper wire is submerged in silver nitrate solution, the copper
reduces the silver(I) ions and the surrounding liquid takes on the
characteristic blue of a copper(II) solution.
Note that although a reaction may be shown to be spontaneous under
standard conditions, this may not be the case in non-standard
conditions and, furthermore, the rate of the reaction may be very slow
due to a high activation energy barrier.
R2.1 How much?: The amount of chemical change
When is it useful to use half-equations?

Redox reactions involve electron transfer; one or more reactants lose electrons which are accepted by other
reactants. The loss of electrons by a reactant is known as oxidation; the gain of electrons by a reactant is
known as reduction. So half equations can be used to quickly determine which species is oxidized and which
is reduced.
The loss and gain of electrons occurs simultaneously, so oxidation and reduction processes cannot occur
independently of each other.
Reduction processes and oxidation processes can be represented by half-equations. The sum of the two half-
equations is used to generate the redox (net ionic) equation.
Half-equations are probably best used to describe redox reactions that involve ionic substances and electron
transfer, for example,
Formation of lithium bromide via a synthesis reaction:
Half-equations: 2Li(s) → 2Li+(s) + 2e− and Br2(l) + 2e− → 2Br−(s)
Redox equation: 2Li(s) + Br2(l) → 2LiBr(s)
Formation of silver from a displacement reaction involving copper and aqueous silver(I) ions:
Half-equations: 2Ag+(aq) + 2e− → 2Ag(s) and Cu(s) → Cu2+(aq) + 2e−
Redox (ionic) equation: 2Ag+(aq) + Cu(s) → Cu2+(aq) + 2Ag(s)
Other types of reactions that can be appropriately described by half-equations include corrosion, metals
reacting with dilute acids and reactions occurring in electrolytic cells and voltaic cells.
Half-equations are much less appropriate for reactions involving non-polar molecules and molecules with
low polarity.
Consider the reaction between hydrogen and ethane to form methane:
C2H6(g) + H2(g) → 2CH4(g)
It makes little chemical sense to refer to the hydrogen here as a proton (H+), or to consider the basically
neutral carbon atom as a quadruply charged anion (C4−).
How does the molar volume of a gas vary with changes in temperature
and pressure?
Themes S1.5 Ideal gases
The molar volume of a gas is simply V/n (volume of gas divided by amount of gas, in moles).
Rearranging the ideal gas equation, pV = nRT, gives:

𝑉𝑉 𝑅𝑅𝑅𝑅
=
𝑛𝑛 𝑝𝑝
This relationship indicates that the molar gas volume is proportional to absolute temperature and inversely
proportional to pressure: double the temperature and the molar volume doubles; double the pressure and the
molar volume is halved.
The table shows values of the molar volume of an ideal gas under a variety of common conditions.
Temperature Pressure Molar volume
0 K 0 0
0 °C 1 atm 22.414 0 dm3 mol−1
273 K 1.013 × 105 Pa 2.241 40 × 10−2 m3 mol−1
0 °C 1 bar 22.7110 dm3 mol−1
273 K 105 Pa 2.27110 ×10−2 m3 mol−1
25 °C 1 atm 24.4654 dm3 mol−1
298 K 1.013 × 105 Pa 2.44654 × 10−2 m3 mol−1
25 °C 1 bar 24.7896 dm3 mol−1
298 K 105 Pa 2.47896 ×10−2 m3 mol−1
In what ways does Avogadro’s law help us to describe, but not explain,
the behaviour of gases?
Themes Structure 1.4 Counting particles by mass
Nature of Theories
Science
Avogadro’s law states that equal volumes of all gases, at the same temperature and pressure, have the same
number of molecules (or atoms if a noble gas).
It follows that, for a given gas at constant temperature and pressure, the volume and amount are directly
proportional and the law can be written mathematically as V ∝ n, where V is the volume of the gas and n the
𝑉𝑉 𝑉𝑉
amount of gas in moles. It can also be written as 1 = 2 , where the subscripts indicate paired values of the
𝑛𝑛1 𝑛𝑛2
variables.
As with other scientific laws, these concise verbal and mathematical statements of the relationship between
volume and amount of gas do not explain why the relationship exists, they simply describe it.
It can help us describe the way blowing into a balloon increases the volume of the balloon (we are adding
more molecules, the flexible material of the balloon allows pressure to equalize and there is no significant
temperature change),but does not explain why this happens.
A full explanation of Avogadro’s law requires the use of molecular kinetic theory. This is an example of the
difference between a law (an empirical regularity, that is, a mere description of nature) and a theory (a model
that provides an explanation of why the law should be true).
What errors may cause the experimental yield to be a higher and b

lower than the theoretical yield?
Inquiry
Inquiry process 1 Designing
processes
Inquiry process 2 Interpreting results
Inquiry process 3 Evaluating
No reactions can be 100% efficient and many industrially important reactions give low yields.
There are various reasons why yields are less than 100% including:
• The reactants may not be totally pure.
• Some of the product may be lost during transfer of the chemicals from one container to another when
the product is separated and purified.
• There may be competing side reactions in which the reactants form different products.
• The reaction does not go to completion because some of the reactants may not react because the
reaction is so slow or because it reaches equilibrium.
Experimental yields apparently greater than 100% are possible if the measured product of the reaction
contains impurities, solvent or a catalyst that cause its mass to be greater than it actually would be if the
product was pure. When chemists synthesize a desired chemical, they need to purify the products of the
reaction.
The atom economy and the percentage yield both give important
information about the ‘efficiency’ of a chemical process. What other
factors should be considered in this assessment?
Themes
S2.4 From models to materials
R2.2 How fast? The rate of chemical change
To ensure a chemical process is ‘green’ involves making choices about reactants, solvents and reaction
conditions that are designed to reduce resource consumption and waste production.
Chemists will need to consider how to carry out the chemical process or synthesis so that it will not consume
excessive amounts of resources, use less energy and be more economical. The synthesis should not produce
large amounts of toxic or harmful by-products, and ideally will require milder reaction conditions.
Energy efficiency is increased if chemical reactions are carried out at ambient temperature and pressure.
Separation and purification operations should also be designed to minimize energy consumption and material
use. Another approach to reducing energy usage is by the use of catalysts.
The use of green chemistry principles in an organic synthesis starts with the selection of the starting
chemical substances, known as feedstock. Most organic compounds used as feedstock are derived from
crude oil. A potential green chemistry approach would be to replace these petrochemicals with chemicals
derived from biological sources such as plants. This approach may be more sustainable as, apart from the
resource being renewable, the refining of organic compounds from biomass is less polluting than the refining
of crude oil.
Another green chemistry approach is to select safer reagents. This may involve choosing a less reactive or
less toxic oxidizing reagent for an oxidation step. For example, sodium chlorate(I) (bleach) can sometimes
be used instead of the highly toxic and potentially carcinogenic mixture of dichromate(VI) ions and sulfuric
acid. In some reactions, it is possible to use enzymes to carry out a chemical reaction. Enzymes generally work
at ambient temperatures and so also increase the energy efficiency of the process.
Another important metric in chemical industries is the E factor. It is defined as the ratio of mass of waste per
mass of product. In the pharmaceutical industry, product tonnage varies from 10 to 103 tonnes and the E
factor ranges from 25 to 100. By comparison, crude oil refining and the production of bulk chemicals are
relatively ‘clean’ processes owing to the widespread use of catalysis.
The pharmaceutical industry, where almost all products contain carbon, also considers the carbon efficiency
of processes.
amount of carbon in product
Carbon efficiency =
total amount of carbon present in reactants
R2.2 How fast?: The rate of chemical change
What is the relationship between the kinetic molecular theory and

collision theory?
matter
The kinetic molecular theory is based on the following simplifying assumptions about the nature of gas
molecules (that is, ideal behaviour):
1 A gas is composed of many identical point-like particles, moving in random directions at high velocity,
separated by large distances
2 The gas molecules undergo perfectly elastic collisions (no loss of kinetic energy) with each other and the
walls of the container, but otherwise do not interact
From these simplifying assumptions, the ideal gas law (pV = nRT) can be derived.
Collision theory is based on the kinetic theory of gases and is used to explain how chemical reactions occur
when molecules collide with sufficient energy and in the correct orientation.
Simple collision theory can be modified and extended to reactions in solution. In solutions, which contain
solvated molecules and ions rather than simple molecules or atoms, interactions are known as encounters
rather than collisions. It would be expected that encounter rates should be smaller than collision frequencies
because the solvent molecules reduce the collision rate between reactants. However, encounters may be more
likely than collisions in cases where molecules are trapped in a temporary ‘cage’ of solvent molecules.
HL only
The collision theory can be used to derive the rate constant for bimolecular gas-phase reactions. This is equal
to the rate of successful collisions, which in turn depends on the fraction of successful collisions multiplied
by the overall collision frequency.
What are the features of transition elements that make them useful as
catalysts?
Transition elements are d block elements that form at least one cation with a partially filled d subshell and
typically exist in more than one oxidation state. This ability to makes them particularly useful as catalysts.
An example is the decomposition (disproportionation) of hydrogen peroxide, H2O2, catalysed by

manganese(IV) oxide, MnO2.
This is thought to occur via the free-radical chain reaction shown in the sequence of steps (1) – (5) below.
Note that manganese starts in the +4 oxidation state, is reduced to the +3 oxidation state in the first step, and
is oxidized back to the +4 state at step (4).
Mn4+ + H2 O2 → H + + Mn3+ + HO∙2 (1)
HO∙2 + H2 O2 → H2 O + O2 + HO∙ (2)
HO∙ + H2 O2 → H2 O + HO∙2 (3)
HO∙ + Mn3+ → Mn4+ + OH − (4)
H + + OH − → H2 O (5)
When the equations are combined and the species that appear on both sides are cancelled out (note that step
(2) needs to be multiplied by 2 in order to cancel the free radical species), the net result is the
disproportionation of hydrogen peroxide:
2H2 O2 → 2H2 O + O2
In the solid phase, transition metals and their compounds can also catalyse reactions by adsorbing reagents
(very often gases) onto their surface and activating them. The catalysis can be described in terms of the
transition atoms or cations surrounded by ligands on the surface of a catalyst.
The reaction between ethene and hydrogen to form ethane on the surface of a metal catalyst (usually hot
nickel) is a well studied and industrially important example of a transition element acting as a heterogeneous
catalyst.
Such heterogeneous catalysis occurs in five stages:
1 diffusion of the reagent gases to the surface of the transition metal (or compound)
2 adsorption of the reagents on the surface
3 reaction between the adsorbed species
4 desorption of the products
5 diffusion of the products away from the surface.
What variables must be controlled in studying the effect of a factor on

the rate of a reaction?
Tools Tool 1 Measuring variables and Applying
techniques
The factors that affect the rate of a reaction are:
1 concentration (or pressure in the case of gas-phase reactions)
2 surface area (which may depend on the physical state or phase of the reactants)
3 temperature
4 the presence or absence of a catalyst.
When studying the effect of one of these variables on the rate of reaction, the other three variables must be
held constant (that is, controlled) in order to ensure a fair test.
If investigating the effect on reaction rate of a different variable, such as light intensity, all four of these
variables need to be held constant as the light intensity is systematically varied.
What experiments measuring reaction rates might use time as a a

dependent and b an independent variable?
Tools Tool 1: Measuring variables
a Time is used as a dependent variable in a so-called

clock reaction (or chemical clock).
A clock reaction is one in which a mixture of
chemical compounds leads to the onset of an
observable physical property after a period of time
(called the induction time).
In iodine clock reactions, an iodine-containing
species is mixed with suitable redox reagents in the
presence of starch. After a delay, known as the
induction time, the solution turns blue-black due to
the formation of the triiodide–starch complex. The
induction time is predictable if the reagent concentrations are accurately known.
Another reaction which is studied using time as a dependent variable is the slow redox reaction between
sodium thiosulfate and hydrochloric acid, which produces a precipitate of solid sulfur. If the vessel
containing the reaction mixture is placed on a piece of paper marked with a cross, the cross will be
obscured from view as the precipitate becomes thicker, and the time taken for this to occur can be
recorded.
In both these cases, the time measured is the time until the ‘signal’ appears rather than the time taken for
the reaction to stop or reach completion (which is determined by the amount of the limiting reagent).
Since reaction rate and time are inversely proportional, taking the reciprocal of the measured time gives a
relative rate that is proportional to the reaction rate.
Systematically changing the starting concentrations or temperature and measuring the reaction time can
be used to establish a rate equation or activation energy for the reaction.
b Any experiment which monitors the concentration of a reactant or product (or suitable proxy variable
such as absorbance, conductivity, mass change, gas pressure or volume) over time uses time as an
independent variable.
How can graphs provide evidence of systematic and random error?

Tools Tool 3: Graphing
Inquiry Inquiry process 3: Evaluating
processes
Nature of Patterns and trends
Science
The diagram shows four graphs of absorbance versus concentration (Beer’s law calibration curves).
A Beer’s law calibration curve should be a straight line passing through the origin showing that absorbance
and concentration are directly proportional.
In the first graph, a, the scatter of the points about the line of best fit (both above and below) is indicative of
random error due to imprecision in the measuring instrument. The displacement of the y-intercept from the
origin shows that the absorbance readings are systematically higher than expected, which could be because
of a coloured impurity in the solution, but is more likely to be because the colorimeter has not been properly
calibrated to read zero absorbance for the pure solvent (known as a blank).
In the second graph, b, the systematic error is still present, but the amount of random error is significantly
reduced (the results are more precise) as evidenced by the closeness of the data to the line of best fit.
In the third graph, c, the systematic error has disappeared, but the scatter of the points is evidence for random
error (a lack of precision).
In the fourth graph, d, there is little evidence of systematic or random error: the data points fit closely to the
line of best fit which passes through the origin as expected.
Concentration changes in reactions are not usually measured directly.

What methods are used to provide data to determine the rate of
reactions?
Tools
Tool 1: Applying techniques
Tool 3: Applying general mathematics
Inquiry Inquiry process 2: Collecting data
processes
It is sometimes possible to measure the change in concentration of a reactant directly by, for example, acid–
base titration of a sample of the reaction mixture. More usually, another variable is monitored as a proxy for
the concentration of a reactant or product. There are a wide range of chemical techniques ending in -metry,
indicating that they are used to measure a particular variable. Some of these are shown in the table.
Technique Quantity measured Example
gravimetry mass of gas released mass lost by a flask containing dilute acid and
metal carbonate on an electronic balance
colorimetry quantity of light of a particular change in the absorbance of a solution in which
wavelength absorbed by a colourless iodide is oxidized to yellow-brown
coloured solution iodine
barometry gas pressure pressure change in a fixed volume when an acid is
reacted with a carbonate
volumetry volume of gas volume of gas measured by downward
displacement of water in the reaction between
dilute acid and a reactive metal
polarimetry rotation angle of plane- change in optical rotation as sucrose is hydrolysed
polarized light to form glucose and fructose
conductometry conductivity of an ionic change in conductivity of solution during a
solution nucleophilic substitution reaction
thermometry temperature change in temperature of a commercial heat pack
spectrophotometry radiation absorbed by a sample change in the absorbance of a solution in which
at a particular wavelength purple manganate(VII) ions are reduced to pale
pink manganese(II) ions
turbidimetry the cloudiness of a solution reaction between sodium thiosulfate and
hydrochloric acid
In some cases the measured variable can be readily converted to a concentration. For example, in
colorimetry, a Beer’s law calibration curve of absorbance versus concentration can be used to interpolate the
concentration from a measured value of absorbance.
In other cases it may be necessary to infer a rate of reaction directly from the gradient of a time series plot of
the measured quantity. The gradient of such a plot is not equal to the rate of reaction (which should have
concentration
units of ), but will be directly proportional to the rate.
time
What measurements are needed to deduce the order of reaction for a

specific reactant?
Tools
Tool 1: Measuring variables
Tool 3: Applying general mathematics
Inquiry
Inquiry process 2: Interpreting results
processes
In order to deduce the order of reaction with respect to a specific reactant, it is necessary to first measure the
rate of reaction under conditions where the starting concentrations of each of the reactants are accurately
known.
In a second reaction, the concentration of the reactant of interest is changed by a convenient factor (for
example, halved or doubled), whilst keeping the concentrations of all other reactants at the same values as in
the first reaction. The new reaction rate is then determined.
Consider the reaction given by the equation below:
A + B → products
which has the rate equation:

rate = 𝑘𝑘[A]𝑎𝑎 [B]𝑏𝑏
Let us assume that the concentration of A is set at x mol dm−3 in the first experiment and is doubled (to 2x) in
the second experiment. Then:
rate1 = 𝑘𝑘𝑥𝑥 𝑎𝑎 [B]𝑏𝑏
rate2 = 𝑘𝑘(2𝑥𝑥)𝑎𝑎 [B]𝑏𝑏
and
rate2
= 2𝑎𝑎
rate1
If rate does not change in reaction 2, then:

rate2
= 1 = 20
rate1
and the order with respect to A is zero.

Similarly, if the rate doubles, the order with respect to A is 1 (2 = 21 ); and if the rate quadruples, the order
with respect to reactant A is 2 (4 = 22 ).
To determine the order with respect to the other reactants, the procedure is repeated by systematically
changing the concentration of the reactant of interest whilst keeping all other concentrations and conditions
fixed.
What are the rate equations and units of k for the reactions of primary
and tertiary halogenoalkanes with aqueous alkali?
Halogenoalkanes (R–X) undergo nucleophilic substitution in the presence of aqueous alkali. The hydroxide
ion, OH− acts as a nucleophile (electron pair donor) and a halide ion (X−) is the leaving group. The general
equation for such a reaction is:
R − X + OH − → R − OH + X −
A tertiary halogenoalkane reacts via an SN1 (first-order nucleophilic substitution) mechanism in which the
slow step involves dissociation of the R–X bond to form a carbocation (R+) intermediate.
The rate equation is:
rate = 𝑘𝑘[R − X]
Since the rate has units of mol dm−3 s−1 and [R–X] has units of mol dm−3, the rate constant k has units of
reciprocal seconds, s−1. The carbocation intermediate reacts very rapidly with OH− to form the alcohol
product and the hydroxide ion concentration therefore has no effect on the reaction rate.
A primary halogenoalkane reacts via a so-called concerted mechanism in which the rate determining step
involves formation of the C–OH bond at the same time as the C–X bond is breaking.
The transition state is of the form [HO---RCH2---X] −. Since both the halogenoalkane and hydroxide ion are
involved in this slow step, the reaction is second order (SN2), with a rate equation:
rate = 𝑘𝑘[R − X][OH − ]
The units of k, when multiplied twice by mol dm−3, must necessarily give the units of rate, mol dm−3 s−1.
Therefore, allowing x to stand for the units of k, we have:
mol dm−3 s −1 = 𝑥𝑥(mol dm−3 )(mol dm−3 )
mol dm−3 s −1 = 𝑥𝑥(mol2 dm−6 )
mol dm−3 s −1
𝑥𝑥 =
mol2 dm−6
Therefore k has units of mol−1 dm3 s−1.
Which mechanism in the hydrolysis of halogenoalkanes involves an

intermediate?
The first elementary step of the alkaline hydrolysis of a halogenoalkane is the slow formation of an
intermediate (R+) with relatively low energy:
R–X → R+ + X−
R+ is a carbocation intermediate and has a positively charged carbon that is electron deficient. This
intermediate can be studied and isolated and its formation favoured when the halogenoalkane is tertiary.
An alcohol is formed when the carbocation reacts with hydroxide ions, which act as a nucleophile (electron
pair donor) to form a new sigma bond:
R+ + OH− → ROH
This second step is relatively fast since the hydroxide ion and carbocation intermediate have opposite
charges.
This is an SN1 hydrolysis reaction (Substitution, Nucleophilic, unimolecular (molecularity of 1), where the
nucleophile attacks the trigonal planar carbocation.
Why are reaction mechanisms only considered as ‘possible

mechanisms’?
Nature of Models
science
Usually a reaction mechanism is proposed based on an experimental determination of the rate equation for
the reaction. Consider the following reaction:
X + Y →Q
The rate equation for this reaction is:

rate = 𝑘𝑘[X][Y]
The following proposed mechanism is consistent with both the rate equation and the balanced chemical
equation:
X⇌I fast
I + Y →Q slow
However, so is the following mechanism:

X⇌I fast
I→M fast
M + Y →Q slow
In theory we could keep adding intermediate steps to the mechanism above (as long as they involve fast
reactions) without any loss of consistency with the rate equation and chemical equation.
Therefore, it can be argued that mechanisms are never proven, but merely supported by the experimental
evidence. There is also the possibility of having two mechanisms consistent with the kinetic data, for
example: O3(g) + NO(g) → NO2(g) + O2(g) (see page 472).
This is certainly true if the only evidence for the mechanism is from experiments in which concentrations
have been systematically varied and rates of reaction measured.
However, it should be noted that in recent decades physical chemists have developed techniques involving
electron microscopy and very short laser pulses that allow the direct probing of chemical reactions on short
timescales, so determining reaction mechanisms with a high degree of confidence does not contravene any
laws of nature.
Another complicating factor is that sometimes it may be possible for molecules to react via more than one
mechanism at once. For example, a secondary halogenoalkane may react via both SN1 and SN2 reaction
pathways. Should this happen, the rate equation data would not be consistent with a purely first or second
order mechanism.
What is the relative effect of a catalyst on the rate of the forward and
backward reactions?
Themes R2.3 How far? The extent of chemical change
Catalysts function by providing an alternate reaction mechanism or pathway that has a lower activation
energy than would be found in the absence of the catalyst. In some cases, the catalysed mechanism may
include additional steps involving low-energy intermediates. This lower activation energy results in an
increase in rate.
A catalyst decreases the activation energy for both the forward and the reverse reactions by the same
magnitude and hence increases the rate of both the forward and the reverse reactions to the same degree.
Consider the reaction:
[C][D]
A +B → C + D K =
[A][B]
that can be catalysed through the production of an intermediate X in a two-step process:

[X]
A → X K1 =
[A]
[C][D]
X + B → C + D K2 =
[X][B]
but [X] = K1 × [A]

[C][D]
so K2 =
𝐾𝐾1[A][B]
[C][D]
and K1 × K2 = = K
[A][B]
The equilibrium constant for the overall reaction is unchanged showing that, while the catalyst allows the
process to reach equilibrium more rapidly, it has no effect on the position of the equilibrium.
HL only
𝑘𝑘
The value of K is equal to the ratio 𝑘𝑘 f , where kf and kr are the rate constants for the forward and reverse
r
reactions, respectively. Using the Arrhenius equation, we can show that this ratio is unaffected by the
presence of a catalyst.
Let us assume a simple first-order: reaction:
reactant → product
which has the following parameters:

Enthalpy change, ΔH = −20 kJ mol−1
Pre-exponential (Arrhenius) factor, A = 100 s−1
Ea(forward) = 50 kJ mol−1
Ea(reverse) = 70 kJ mol−1
T = 300 K
Then:
−𝐸𝐸a
𝑘𝑘f = 𝐴𝐴e 𝑅𝑅𝑅𝑅
−50 000
= 100e8.314×300
= 1.97 × 10−7 s −1
and
−𝐸𝐸a
𝑘𝑘r = 𝐴𝐴e 𝑅𝑅𝑅𝑅
−70 000
= 100e8.314×300
= 6.48 × 10−11 s −1
So:
𝑘𝑘f 1.97×10−7 s−1
K= = = 3037
𝑘𝑘r 6.48×10−11 s−1
If a catalyst is added that lowers the activation energy by 20 kJ mol−1, we obtain:

−𝐸𝐸a
𝑘𝑘f = 𝐴𝐴e 𝑅𝑅𝑅𝑅
−30 000
= 100e8.314×300
−4
= 5.98 × 10
s−1
−𝐸𝐸a
𝑘𝑘r = 𝐴𝐴e 𝑅𝑅𝑅𝑅
−50 000
= 100e8.314×300
= 1.97 × 10−7 s −1
The ratio of kf to kr , and hence the equilibrium constant, remains unchanged.

e𝑥𝑥
An alternative approach is to note that, in both cases, the activation energies differ by 20 kJ mol−1. Since e𝑦𝑦 =
𝑘𝑘f
e𝑥𝑥−𝑦𝑦 , the ratio equals e20000/(8.314×300) with or without the catalyst.
𝑘𝑘r
For a system at equilibrium and in the presence of a catalyst the forward and reverse reaction rates are both
faster than in the uncatalysed system, but the ratio of the rates is independent of whether a catalyst is present
or not.
R2.3 How far?: The extent of chemical change
How does the value of K for the dissociation of an acid convey

information about its strength?
A weak, monoprotic acid HA dissociates in water according to the equilibrium equation:

HA + H2 O ⇌ H3 O+ + A−
An equilibrium constant, K, for the process can be written as follows:

[H3 O+ ][A− ]
𝐾𝐾 =
[HA][H2 O]
However, since the concentration of the water solvent remains essentially constant (~55.6 mol dm−3), it can
be combined with K to produce another constant Ka (= K × [H2O]) called the acid dissociation constant. Ka.
[H3 O+ ][A− ]
𝐾𝐾a =
[HA]
Recall that equilibrium constants do not possess units (they are dimensionless constants expressed in terms
of activities (relative concentrations) which do not have units).
The larger the Ka value, the stronger the acid as this indicates a greater concentration of H3 O+ . Similarly, the
smaller the Ka value, the weaker the acid. Ka values typically vary over many orders of magnitude, so acid
strength is often represented using pKa values instead, where pKa= −log10 Ka.
Acid Formula Ka pKa
Hydrochloric HCl 1.3 × 10 6
−6.11
Trichloroethanoic CCl3COOH 2.19 ×10−1 0.66
Hydrofluoric HF 6.6 × 10−4 3.18
Methanoic HCOOH 1.78 × 10−4 3.75
Ethanoic CH3COOH 1.74 × 10−5 4.76
Phenol C6H5OH 1.02 × 10−10 9.99
The very large Ka value (and hence negative pKa value) for hydrochloric acid shows it is a strong acid and
can reasonably be assumed to dissociate virtually fully (100%) in aqueous solution. All of the other acids are
weak acids which undergo partial or incomplete dissociation.
For the weak acids we can only talk about their relative strength: although methanoic acid is stronger than
ethanoic acid (as indicated by its higher Ka and lower pKa), that does not make it a strong acid.
For polyprotic acids such as phosphoric(V) acid (H3PO4) a Ka value can be determined for the successive
stepwise dissociation of each acidic proton (H+ ion):
[H3 O+ ][H2 PO4− ]
H3 PO4 + H2 O ⇌ H3 O+ + H2 PO−
4 𝐾𝐾a1 = = 6.9 × 10−3
[H3 PO4 ]
[H3 O+ ][HPO2−4 ]
H2 PO− + 2−
4 + H2 O ⇌ H3 O + HPO4 𝐾𝐾a2 = = 6.2 × 10−8
[H2 PO−
4 ]
[H3 O+ ][PO3−
4 ]
HPO2− + 3−
4 + H2 O ⇌ H3 O + PO4 𝐾𝐾a3 = 2− = 4.8 × 10−13
[HPO4 ]
As is typical of weak acids, the acid dissociation constant decreases (and pKa increases) as each subsequent
proton is lost, meaning that the order of decreasing acid strength is: H3PO4 > H2PO4− > HPO42−.
Why do catalysts have no effect on the value of K or on the equilibrium

composition?
A catalyst greatly increases the rate of a chemical reaction by providing a new reaction pathway which has a
lower activation energy than the uncatalysed pathway. The pathway of a reversible reaction is the same for
both the forward and backward directions: it is just reversed. The transition state is the same regardless of
whether the reaction is proceeding backwards or forward.
The catalyst increases the forward and backward reactions to the same extent so adding a catalyst does not
affect the relative rates of the two reactions. It cannot, therefore, affect the position of equilibrium and Le
Châtelier’s principle does not apply.
HL only
The composition of a reaction system at equilibrium, and hence the value of the equilibrium constant, K,
depends only on the Gibbs free energy change of the reaction and not on the height of the activation energy
barrier between reactants and products.
Specifically:
Δ𝐺𝐺 ⦵ = −𝑅𝑅𝑅𝑅ln 𝐾𝐾
which rearranges to give:

Δ𝐺𝐺 ⦵
𝐾𝐾 = e− 𝑅𝑅𝑅𝑅
By lowering the activation energy, a catalyst increases the rate at which equilibrium is attained, but it does
not have any effect on the equilibrium composition or the value of K.
How does the equilibrium law help us to determine the pH of a weak

acid, weak base or a buffer solution?
Weak acids
A weak, monoprotic acid HA dissociates according to the equation:
HA + H2 O ⇌ H3 O+ + A−
The equilibrium constant for this reaction is given by the expression:

[H3 O+ ][A− ]
𝐾𝐾a =
[HA]
and is known as the acid dissociation constant, Ka.

Since H3O+ and A− are produced in solution in a 1:1, ratio the Ka expression above can be rewritten as:
[H3 O+ ]2
𝐾𝐾a =
[HA]
Rearranging gives:
[H3 O+ ]2 = 𝐾𝐾a × [HA]
Therefore:
[H3 O+ ] = �𝐾𝐾a × [HA]
and the pH can be determined by taking the negative logarithm (to the base 10) of each side of the equation:
pH = −log (�𝐾𝐾a × [HA])
This approach assumes that the acid is so weak that the concentration of the weak acid [HA] in the solution
is not reduced by dissociation – so it is an approximation.
The approximation is reasonable for most weak acids, which only dissociate to the extent of 1% or less.
Weak bases
A weak base may either be a molecule (B) or an anion (B−):
B(aq) + H2O(l) ⇌ BH+(aq) + OH–(aq)
B−(aq) + H2O(l) ⇌ BH(aq) + OH–(aq)
The equilibrium constant for this reaction is known as the base dissociation constant:
�BH+(aq)�×[OH−(aq)] [BH(aq)]×[OH− (aq)]
Kb = [B(aq)]
or [B− (aq)]
To calculate the pH of a solution containing a weak base, a similar approximation to that of a weak acid is
used, giving: [OH−(aq)] = �𝐾𝐾b × [B(aq)] or [OH−(aq)] = �𝐾𝐾b × [B− (aq)].
This leads to the similar looking formula below:
pOH = −log (�𝐾𝐾b × [B])
Alternative method
If provided with the Ka of its conjugate acid, you can also determine the pH of a weak base using the method
illustrated by the following worked example.
Calculate the pH of a 0.100 mol dm−3 aqueous solution of the weak base aminomethane, CH3NH2;
Ka(CH3NH3+) = 2.19 × 10−11.
The equilibrium established when aminomethane dissolves in aqueous solution and the Ka expression for its
conjugate acid are as follows:
CH3 NH2 + H2 O ⇌ CH3 NH3 + + OH −
[H3 O+ ][CH3 NH2 ]

𝐾𝐾a (CH3 NH3+ ) =
[CH3 NH3+ ]
Since OH− and CH3NH3+ are formed in solution in a 1:1 ratio:

[CH3 NH3+ ] = [OH − ]
We can also assume, since the degree of dissociation of CH3NH2 is very small (as it is a weak base), that:
[CH3 NH2 ] ≈ 0.100 mol dm−3
Combining the above two assumptions with the Ka expression above, we obtain:
0.100 × [H3 O+ ]
𝐾𝐾a [CH3 NH3+ ] =
[OH − ]
Since [H3O+] × [OH−] = Kw = 1.00 × 10−14 substituting for [OH−] in the expression above gives:
0.100 × [H3 O+ ]2
𝐾𝐾a [] =
𝐾𝐾w
Rearrangement of this equation gives a general formula which can be used to calculate the pH of any weak
base solution:
𝐾𝐾a × 𝐾𝐾w
[𝐻𝐻3 O+ ] = �
[base]
For the example above:

2.19 × 10−11 × 1.00 × 10−14
[H3 O+ ] = � ; pH = 11.8
0.100
Buffers
A buffer is a solution that resists change in pH when small amounts of a strong acid or alkali are added over
a certain range or when the solution is diluted.
A buffer solution contains a weak acid and its conjugate base, or a weak base and its conjugate acid, in close
to equimolar amounts.
Buffers may be acidic or alkaline depending on whether their pH is greater than or less than 7.
The precise pH of the buffer will depend on which species (acid or base) is present in excess. A buffer can be
formed by adding a known number of moles of each species to solution, by the partial neutralization of a
weak base by a strong acid, or by the partial neutralization of a weak acid by a strong base.
To determine the pH of a buffer we start once again from the chemical equation for the dissociation of a
weak acid in aqueous solution:
HA + H2 O ⇌ H3 O+ + A−
The corresponding Ka expression is:

[H3 O+ ][A− ]
𝐾𝐾a =
[HA]
Taking negative logs (in base 10) of both sides and recalling that log (a × b) = log(a) + log(b) gives:
[A− ]
−log 𝐾𝐾a = − log [H3 O+ ] − log
[HA]
But −log Ka and −log [H3O+] are simply pKa and pH respectively, so:
[A− ]
p𝐾𝐾a = pH − log
[HA]
Making pH the subject of the formula and remembering that [A–] and [HA] are a strong base and weak acid,
respectively, yields the Henderson–Hasselbalch equation, which can be used to determine the pH of any
buffer system, provided we know the concentrations of the weak acid and base, and the pKa of the weak acid:
[base]
pH = p𝐾𝐾a + log 10
[acid]
When the weak acid and weak base concentrations are exactly equal a buffer is formed with pH = pKa, since
log (1) = 0. A buffer will be effective in the pH range given by pKa ± 1. If the pH is higher than pKa the
conjugate base is present in excess; if the pH is lower than pKa the conjugate acid is present at a higher
concentration than the conjugate base.
How can Gibbs energy be used to explain which of the forward or

backward reaction is favoured before reaching equilibrium?
Themes R1.4 Entropy and spontaneity
The second law of thermodynamics states that the entropy of the universe tends to a maximum and,
therefore, any spontaneous chemical process is accompanied by an increase in the entropy of the universe.
The standard Gibbs free energy change of a reaction is related to the equilibrium constant by the equation:
Δ𝐺𝐺 ⦵ = −𝑅𝑅𝑅𝑅ln 𝐾𝐾
ΔG⦵ is the difference in Gibbs free energy between the pure products and pure reactants under standard
conditions (of pressure, temperature and molar concentration where applicable).
Δr 𝐺𝐺 ⦵ = ΣΔ𝐺𝐺 ⦵ (products) − ΣΔ𝐺𝐺 ⦵ (reactants)
As a reaction proceeds towards equilibrium the difference in Gibbs energy (ΔG) between reactants and
products decreases, until at equilibrium the difference in Gibbs energy between reactants and products equals
zero.
If a system is not at equilibrium, ΔG and the reaction quotient Q can be used to decide in which direction the
reaction will proceed to reach equilibrium. ΔG is related to Q by the equation:
𝑄𝑄
Δ𝐺𝐺 = 𝑅𝑅𝑅𝑅ln
𝐾𝐾
If ΔG < 0, then K > Q, and the reaction will proceed to the right to reach equilibrium.
If ΔG > 0, then K < Q, and the reaction will proceed to the left to reach equilibrium.
If ΔG = 0, the K = Q and the reaction is at equilibrium.

IB-Chemistry LQ Answers-4

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Chemistry for the IB Diploma – Answers

Answers to linking questions

How do intermolecular forces influence the type of mixture that forms

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Figure S2.A6 Electron density map of lithium

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