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AP CHEMISTRY

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UNIT 01: Atoms, Elements & Periodicity

TOPIC 1C: Empirical & Molecular Formula

TOPIC 1D: Pure & Impure

Elements, atoms, mixtures and compounds

An element is defined as a substance that cannot be broken down into other substances by
chemical means. Any single element is comprised of only one type of atom. The elements are
displayed on the periodic table.

A compound is formed when a number of these elements bond together. Compounds always
have a fixed composition of atoms, i.e., they always contain the same, definite amount of each
element’s atoms. For example, a water molecule always contains two hydrogen atoms bonded to
one oxygen atom, and it always has the formula, H2O. When the ratio of each type of atom is
fixed within a compound, so is the ratio of the masses of the atoms. If that ratio changes, then the
chemical formula changes, and the substance ceases to be water. All pure substances are either
elements or compounds.

Unlike a pure compound or element, a mixture has varying composition and is made up of a
number of pure substances. Mixtures are either;

Homogeneous, with a uniform in composition throughout a given sample but with a composition
and properties that vary from one sample to another, for example, a solution of salt water taken
from different bodies of water in different locations, or

Heterogeneous, with separate, distinct regions within the sample with a composition and
properties that vary from one part of the mixture to another, for example, a chocolate chip cookie.

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Relative atomic mass and the periodic table

Each element has an atomic mass number displayed on the periodic table. In the periodic table
shown below, atomic numbers are printed above the symbol and atomic masses below.
GROUP
Period
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 2
1 H He
1 4
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
7 9 11 12 14 16 19 20
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
23 24 27 28 31 32 35.5 36
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39 40 45 48 51 52 55 56 59 59 64 65 70 73 75 79 80 84
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
86 88 89 91 93 96 99 101 103 106 108 112 115 119 122 128 127 131
57-71
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
133 137 178 181 184 186 190 192 195 197 201 204 207 209 210 210 222
89-103
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra † Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
223 226

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
*Lanthanides La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
139 140 141 144 147 150 152 157 159 163 165 167 169 173 175
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
†Actinides Ac† Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
226 232 231 238 237 242 243 247 251 251 254 253 256 254 257

Formulae of compounds

The chemical formula of a compound shows the exact ratio of the atoms of the elements that are
present in the compound. The numbers of each element are recorded using a subscript to the
right of the element symbol. When only one atom is present, the subscript of ‘1’ is understood and
assumed and therefore not written. For example, H2O means 2 hydrogen atoms associated with
1 oxygen atom.

Percentage composition in chemical formula

To determine the percentage by mass composition of an individual element within a compound,

simply express the mass of each element as a percentage of the total mass of the compound.

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Empirical formula

The empirical formula of a compound is the simplest whole number ratio of the atoms of each
element in that compound. Entirely different and unrelated compounds, with entirely different
molecular formula (see below), may have the same empirical formula. For example, benzene
C6H6, ethyne C2H2 and 1,3,5,7-cyclooctatetraene C8H8, are very different compounds but they
each have a 1:1 ratio of C to H atoms in their molecular formula, so all have an empirical formula
of CH.

Empirical formulae can be calculated from mass data. There is a simple method to follow.

a. Take the percentage of each element present in the compound and assume a sample
mass of 100 g, thus converting the %’s to a mass in g of each element.

b. Find the atomic mass of each element on the periodic table.

c. Divide the mass in grams by the atomic mass number. This gives a quantity known
as moles.

d. Find the smallest number of moles calculated in c., and divide all the results of the
calculations in c. by that number, i.e., find the ratio of the moles.

N.B. Avoid rounding up or down too much at this stage, and be lenient with significant
figures.

e. The results from d. should be in a convenient, whole number ratio and gives the
empirical formula, i.e., the empirical formula is a ratio of the moles of the elements
present.

N.B. It may be that the ratio includes a recognizable decimal (a fraction) such as .500,
.333 or .250 etc. If so, then multiply all numbers by 2, 3 or 4 as appropriate, in order to
remove the decimal.

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For example, to calculate the empirical formula for the compound containing 40.1% carbon,
6.60% hydrogen and 53.3% oxygen by mass, following this method.

C H O
a. Assuming 100g sample, the % by mass 40.1 6.60 53.3

b. RAM (from periodic table) 12.011 1.0079 16.00

c. % by mass ÷ RAM 3.34 6.55 3.33

d. Divide by smallest 1 2 1

e. Empirical formula C1H2O1 or CH2O

Task 1.1

1. Calculate the empirical formulae of the three oxides of iron shown below.

(a) 77.78% Fe, 22.22% O

(b) 70.00% Fe, 30.00% O
(c) 72.40% Fe, 27.60% O

2. Which of the following are possible empirical formulae? Explain your answer.

CH, CH2, C4H4, CH3O, C3H6O2

3. Three samples of sodium chloride are analyzed and found to contain differing percent
by mass of chlorine. What does this information alone, tell us about the three
samples?

Molecular formulae

Once the empirical formula has been established, and given further appropriate data, the
molecular formula of a compound can be calculated. The molecular formula tells us exactly how
many atoms of each element are present in the compound rather than just the simplest whole
number ratio. The molecular formula is a simple multiple of the empirical formula. In the example
above, an empirical formula of CH2O has a total mass of 30 gmol-1 (12.011 + 1.0079 +1.0079 +
16.00), but could have a molecular formula that is any whole number multiple of CH2O, for
example, CH2O, C2H4O2, C3H6O3 etc.

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To find the molecular formula it is necessary to know the molar mass or relative molecular mass
(RMM) of the compound. Given that the molar mass in this example is found to be 60 gmol-1, it is
clear that the molecular formula is C2H4O2, i.e., two times the empirical formula.

Task 1.2

1. A hydrocarbon (a compound containing only hydrogen & carbon) is found to be

7.690% H and 92.31% C by mass. Calculate its empirical formula.

2. The same hydrocarbon as in question 1, has a molar mass of 78.00 gmol-1. What is the
molecular formula of the compound?

3. An impure sample of the same hydrocarbon is found to have a % by mass of carbon of

80.00 %. Is this observation consistent with an impurity that contains no carbon?
Explain your answer.

TOPIC 1A: The Mole

Avogadro’s number and the mole concept

In chemistry, amounts of substances are measured in a quantity called moles (mols). The mole is
a standard number of particles (atoms, ions, formula units or molecules) and is defined as the
amount of any substance that contains the same number of particles as there are C12 atoms in 12
g of the C12 isotope.

The actual number of particles in a mole, known as the Avogadro constant (or number), is found
to be 6.022 x 1023 particles per mole, and has the unit mol-1. For example, 12 g of carbon atoms
23
contains one mole of C12 atoms, i.e., 6.022 x 10 atoms. If there are 6.022 x 1023 atoms (a huge
number) in just 12 g of carbon, it means that atoms must be very, very tiny!

Atomic mass units (amu)

Since the mass of an atom is so very tiny, and masses expressed in grams or kilograms would be
infinitesimally small, we often use another unit to express the mass of an individual atom. That
unit is the atomic mass unit or amu. 1 amu has a mass of 1.66 x 10-24 g. The mass number
associated with any given atom is the mass of one of those atoms in amu. So, for example, one
C12 atom has a mass of 12 amu and one atom of Cl35 has a mass of 35 amu. Converting the

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chlorine atom mass to grams we get, (35) (1.66 x 10-24 g) = 5.81 x 10-23 g. This is also a very
small number, so we use the concept of the mole to overcome the problem of handling such
small quantities.

Since 1 mole contains 6.022 x 1023 particles, if we take 1 mole of Cl35 atoms they will have a
mass of (5.81 x 10-23 g) (6.022 x 1023) = 35.0 g.

This is not coincidence, and it means that the mass number associated with any given atom is not
only the mass of a single atom in amu, but also the mass of one mole of those atoms in grams.

The average relative atomic masses of atoms shown on the periodic table can be used to
determine the relative average masses of compounds by simple summation.

Relative Molecular Mass (RMM) or Molar Mass - Found by adding all of the individual RAM’s
together in one molecule of a compound.

Relative Formula Mass (RFM) or Molar Mass - Found by adding all of the individual RAM’s
together in one formula unit of an ionic compound.

Since the mass numbers associated with each element are the masses in g of 1 mole, we can
apply the following relationships to calculate the numbers of moles of any element or compound.

mass of sample mass of sample

Moles of an element = =
RAM Molar Mass

mass of sample mass of sample

Moles of a molecular compound = =
RMM Molar Mass

mass of sample mass of sample

Moles of an ionic compound = =
RFM Molar Mass

Task 1.3

1. What is the mass of one mole of sodium chloride, NaCI?

2. How many moles of Ca atoms are there in 140. g of calcium?
3. How many moles of CuBr2 are there in 0.522 g of copper (II) bromide?
4. How many moles of CO2 molecules are there in 23.0 g of carbon dioxide?
5. How many ‘particles’ are present in each of the chemicals in questions 1-4 above?

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Once we have established how to determine the empirical and molecular formula of compounds,
we can bring those formulae together in chemical equations that summarize chemical reactions.
Since individual formula are molar ratios of atoms, then balanced chemical equations (i.e., those
that conserve atoms and mass) are molar ratios of compounds. If we can calculate the moles of
any one substance in a chemical reaction from its mass, then, by ratio, we can find the moles
(and hence the mass) of any other substance in the balanced equation.

TOPIC 1B: Isotopes and Mass Spectrometry

Relative atomic mass (RAM) or molar mass

Relative atomic mass is defined as the weighted average of the masses of all the atoms in a
normal isotopic sample of the element based upon the scale where 1 mole of atoms of the C12
isotope has a mass of exactly 12.00 g.

Elements occur in nature as a number of different isotopes. Atoms with the same number of
protons and electrons, but different numbers of neutrons are called isotopes. This leads to the
modification of the postulate in Dalton’s atomic theory that claimed all atoms of a given element
were identical, to more accurately state;

All atoms of the same element contain the same number of protons and electrons but may have
different numbers of neutrons.

Since it is the electrons in atoms that affect the chemical properties of a substance, isotopes of
the same element have the same chemical properties.

Task 1.4

1. Consider the following pairs. Does either pair represent a pair of isotopes?

40
(a) K19 and 40Ar18
90
(b) Sr38 and 94Sr38

All periodic tables have atomic mass numbers that are not integers. What does this mean? A
good starting point is to analyze what it does not mean. For example, the atomic mass of Cl is
often quoted on periodic tables as 35.5, and may be represented thus; 35.5Cl17. This does not
mean that there are 17 protons, 17 electrons and 18.5 neutrons in an atom of chlorine. It is not

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possible to have a fraction of a neutron in an atom. So, what does it mean, and where does the
‘0.5’ come from?

The non-integer values mean that there is more than one isotope of chlorine that exists in nature,
in the case of chlorine, 35Cl and 37Cl. A quick calculation shows that these two species have the
same number of protons and electrons, but different, whole numbers of neutrons (18 and 20
respectively). That is, they are isotopes of one another. These isotopes happen to exist naturally
in the approx. abundance, 35Cl, 75 % and 37Cl, 25 %.

A simple calculation can be applied to calculate the average atomic mass when considering all
the isotopes present in a natural sample.

S(% of each isotope) (atomic mass of each isotope)

Average atomic mass =
100

In this case,
((35) (75)) + ((37) (25))
Average atomic mass = = 35.5
100

Another example is provided by boron. Boron has two isotopes, 10B and 11B. They have the
abundance 18.7 % and 81.3 % respectively.

((10) (18.7)) + ((11) (81.3))

Average atomic mass = = 10.8
100

Task 1.5

1. Neon has three isotopes of masses 22, 21 and 20 amu. If the isotopes have the
abundance 8.01 %, 1.99 % and 90.00 % respectively, what is the average atomic mass
of neon atoms?

2. A naturally occurring sample of an element consists of two isotopes, one of mass 85

amu and one of mass 87 amu. The abundance of these isotopes is 71 % and 29 %
respectively. Calculate the average atomic mass of an atom of this element.

3. If the two isotopes of gallium, 69Ga and 71Ga occur in the respective percentages of
62.1 and 37.9, calculate the average atomic mass of gallium atoms.

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Mass spectrometry

As we saw earlier, Dalton’s atomic theory needed to be amended following the discovery of
isotopes. This serves as another example of the amendment of a scientific theory based upon
new evidence.

Mass spectrometry is used to detect isotopes and provide evidence for their existence. In the
simplest of terms, a machine known as a mass spectrometer uses an ionizing beam of electrons
to analyze a sample of an element by turning atoms into positive ions. The resulting individual
ions are then sorted by mass. Since a sample of a single element can contain atoms with
different numbers of neutrons (different isotopes), we can expect a number of distinct ions of
different masses to be identified within the spectrum. Analysis of such data can lead to the
identification of different isotopes and consequently to the calculation of average atomic masses.

Analysis of mass spectra

A typical mass spectrum is shown below, in this example for chromium. Like PES, relative
intensity is plotted on the y-axis, and is a guide to the abundance of each isotope. This time,
mass/charge (M/e) ratio is plotted on the x-axis, and is equivalent to the mass of each isotope.

https://www.sisweb.com/mstools/spectrum.htm

Isotope %
50 4.345
52 83.789
53 9.501
54 2.365

The spectrum was generated from the data above.

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Below is a mass spectrum for chlorine. This is a slightly more complicated example, and includes
data for a diatomic species (Cl2) that you will not see on the AP exam, but is still useful for our
discussions.

http://webbook.nist.gov/cgi/cbook.cgi?Spec=C7782505&Index=0&Type=Mass&Large=on&SVG=on

It can be seen that chlorine apparently has two isotopes, one of mass 35 and one of mass 37,
and that they are in a 3:1 ratio (relative peak height). When chlorine atoms pair together in
chlorine molecules, there are three possibilities for their mass; Cl2 70 (two Cl35 atoms), Cl2 72
(one Cl35 atom and one Cl37 atom) and Cl2 74 (two Cl37 atoms). The relative likelihood of forming
a molecule with a particular mass is influenced by the relative likelihood of encountering the
individual isotopes, meaning that molecules with masses that are made from Cl35 atoms rather
than Cl37 atoms, are more prevalent, simply because Cl35 is three times more abundant than Cl37.

Task 1.6

1. Naturally occurring chlorine molecules, Cl2, have masses of 70, 72 and 74 amu as seen
in the mass spectrum above. They occur in the percentages 56.25%, 37.50% and
6.250% respectively. Use this data to calculate the average atomic mass of chlorine
atoms and to find the relative abundance of 35Cl and 37Cl isotopes.

2. Sketch the mass spectrum that you might expect to observe if bromine were passed
through a mass spectrometer. The two common isotopes of bromine are Br79 and Br81

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that are known to exist in an approx. 1:1 ratio and like chlorine, bromine is known to
form diatomic molecules.

3. The mass spectrum for titanium produces peaks according to the following data. Use
the data to calculate the relative atomic mass of Ti.

m/z 46 47 48 49 50
Relative
8.25 7.44 73.72 5.41 5.18
abundance

4. A typical mass spectrum for Mg contains three peaks at m/z values of 24, 25 and 26
respectively.

(a) What does the existence of three peaks suggest?

(b) The relative intensities of the three peaks (24, 25 and 26) are found to be 63, 8.1
and 9.1 respectively.

(i) What do these data tell us about the isotope with m/z = 24?
(ii) Calculate the relative atomic mass of magnesium.

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TOPIC 1E: Atoms & Electronic Configuration

Rutherford and Bohr models of the atom

The Rutherford model of the atom, where a dense nucleus containing positive protons (and
ultimately neutral neutrons) is surrounded by negative electrons, is based around the attraction
between the oppositely charged protons and electrons, and is governed by Coulombs law.
Coulombs law states that the force between two charged particles, q1 and q2, is inversely
proportional to the square of the distances between them.

q1 q2
Fα
r2

When q1 and q2 have the same sign, the force is repulsive, and when they are of opposite signs,
the force is attractive, i.e., like charges repel, and opposite charges attract.

Bohr adapted Rutherford’s model (sometimes called the solar system model) and suggested that
electrons could only travel in fixed orbits or shells (1, 2, and 3 etc. below) around the nucleus.

Using a device called a spectroscope, it was found that gaseous elements emitted
electromagnetic radiation when heated. The light that was emitted consisted of discrete packets
of energy (quanta), and each element emitted a unique pattern of radiation. It was discovered that
the release of radiation was caused by electrons in the atom absorbing energy and being
promoted to a shell further away from the nucleus (for example, from ‘orbit 1’ to ‘orbit 2‘).

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When the electron falls back to its original, lowest energy shell (the ground state), it releases the
energy that it absorbed when it was promoted to the higher energy shell (the excited state). This
release of energy creates a line in a spectrum.

Since the shells are in fixed positions, the difference in energies between them (and hence the
wavelength of the line in the spectra created by the electron returning to the ground state), is also
fixed. This gives a unique and identifiable pattern for each element.

Sometimes an electron may gain sufficient energy to completely overcome the force of attraction
from the nucleus, and it may be ejected from the atom. The energy required to achieve this is
different for each electron (since all electrons sit at different distances from the nucleus and the
force of attraction is partly dependent upon the distance between the nucleus and the electron),
and is called its ionization energy. Bohr’s model predicted a certain regular arrangement of
electrons, and this model is consistent with a certain, regular pattern of observed ionization
energies.

Electronic configuration

The models that suggested that the electron was a discrete particle, and that there were only
strictly defined fixed ‘orbit’s’ in which electrons travelled, did not explain several of the observed
properties of the atom and electrons. Work by Bohr, marrying classical physics and new quantum
ideas proposed by Planck (and then by de Broglie and others) suggested that the electron also
had some wave-like characteristics. The description of the electron in this wave-particle duality
manner is extremely complex and requires very advanced physics, calculus, other mathematics
and detailed quantum theory that we do not discuss in AP chemistry, but a few notes about
waves may help.

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All electromagnetic radiation may be considered as waves that are defined by the properties of
wavelength and frequency. The wavelength (l) is the distance between two repeating points on a
sine wave.

The frequency (u) is the number of waves that pass a fixed point in a second. Frequency is
measured in units of s-1 or Hertz (Hz). The speed of light (c), can be calculated by considering the
frequency and the wavelength of the electromagnetic radiation.

c = lu

Depending on the value of the frequency and the value of the wavelength, the radiation will fall
somewhere in the electromagnetic spectrum according to the diagram below.

Schrödinger developed the wave idea for atoms and electrons and solved wave equations to
make predictions about where an electron may actually be found in an atom. The result of all this
work, coupled with the Heisenberg uncertainty principle (which states that the momentum and
position of an electron cannot be determined simultaneously meaning it is only possible to predict
where an electron will probably be at any one time rather than knowing its exact whereabouts),
led to the quantum mechanical model of the atom of that we have today, and to the idea of three
dimensional probability maps (rather than a fixed, planet-like orbit) of where any one electron may
be found at any point in time within each of the shells. This idea superseded the simpler version
of fixed orbits provided by Rutherford and Bohr, and serves as an example of the development of
scientific theory based upon new, experimental evidence.

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Orbitals

The three dimensional probability maps predicted by Schrödinger are known as orbitals and they
describe the likely positions (or areas of space) of electrons within the atom. Using the
Rutherford/Bohr model as the basis, the maximum number of electrons present in each shell is
given by 2(n2), where n is the shell number. Using this simple relationship, we find that the
maximum number of electrons in each of the first four shells in any atom is;

Shell number Maximum number of electrons

1 2

2 8

3 18

4 32

Each shell is further divided into sub-shells. The number of sub-shells that are possible within any
given shell is equal to the shell number, and the sub-shells are given the letters s, p, d and f. The
first sub-shell in any shell is an s sub-shell, the second is a p sub-shell, the third is a d sub-shell
and the fourth is an f sub-shell.

Shell number Number of sub-shells Corresponding letter

1 1 s

2 2 s, p

3 3 s, p, d

4 4 s, p, d, f

Each sub-shell is further divided into orbitals. The s, p, d and f sub-shells are split into 1, 3, 5 and
7 orbitals respectively, and each orbital can hold a maximum of two electrons. The number of
orbitals and electrons that are possible in each sub-shell, in each shell, is as follows;
Maximum number of
Sub-shell Number of possible orbitals
electrons
s 1 2
p 3 6
d 5 10
f 7 14

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The Pauli exclusion principle says that all of the electrons in any single atom must be unique, so if
a pair of electrons are in the same orbital as one another, since their shell, sub-shell and orbital
are all the same, they must be distinguished by another method. This is achieved by giving the
electrons an intrinsic property known as ‘spin’. Two electrons in the same orbital are given
opposite spins, often denoted as a pair of arrows, one pointing up and one pointing down, or
sometimes the quantum numbers +½ and –½.

As stated above, the orbitals represent three-dimensional areas of space in the atom, where an
electron may be found, and the s, p, d and f orbitals all have different shapes. s orbitals are
spherical (soccer ball) shaped, p orbitals are dumb-bell (figure of eight) shaped and align
themselves on x, y and z-axes in space, and d & f orbitals have more complicated shapes.

Summary of shells, sub-shells and orbitals

Here is a summary of what has gone in the previous paragraphs;

Max.
Number of Number of
Shell Number of Sub-shell number of
orbitals in electrons in
number sub-shells designation electrons in
sub-shell whole shell
sub-shell
1 1 1s 1 2 2

2s 1 2
2 2 8
2p 3 6

3s 1 2

3 3 3p 3 6 18

3d 5 10

4s 1 2

4p 3 6
4 4 32
4d 5 10

4f 7 14

Rules for filling orbitals (aufbau process)

1. Find out how many electrons are present (refer to the atomic number of the atom and
then consider any charges present caused by the loss or gain of electrons).
2. Lowest energy orbitals are filled first.
The orbitals have ascending energies with 1s having the smallest energy, 2s the next
smallest etc.

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There is pretty significant complication that arises here, which can be accommodated by
considering the 4s orbital as having a slightly lower energy than the 3d orbitals, and
assuming that the 4s orbital is filled before the 3d orbitals. Although this is not really true,
it does lead to the correct prediction of electronic configurations.

Similarly, it is helpful (if not quite correct) to assume that the 5s orbital has a slightly lower
energy than the 4d orbitals and as a result the 5s orbital is filled before the 4d orbital.

3. Hund’s rule of maximum multiplicity states that if there is more than one orbital with the
same energy (described as degenerate orbitals), then one electron is placed into each
orbital before any pairing takes place. All orbitals in the same sub-shell have a similar
energy, for example, all three, 2p orbitals have the same energy and are therefore
degenerate. As a result, if there are three electrons to be placed into the three, 2p
orbitals, then one electron enters the first 2p orbital (x), one enters the second (y) and
one enters the third (z), before any are paired in the x, y or z.

Using the periodic table to determine electronic configuration

This is an extremely powerful tool and requires a slight, but significant modification of the periodic
table. In the table below hydrogen and helium have been moved into groups 1 and 2 respectively.
This is only for the purpose of determining electronic configuration and is not necessarily
appropriate in other circumstances, although H will sometimes appear at the top of group 1,
anyway.
GROUP
Period 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
s BLOCK d BLOCK p BLOCK
1 2
1 H He
1 4
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
7 9 11 12 14 16 19 20
\
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
23 24 27 28 31 32 35.5 36
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39 40 45 48 51 52 55 56 59 59 64 65 70 73 75 79 80 84
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
86 88 89 91 93 96 99 101 103 106 108 112 115 119 122 128 127 131
57-71
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
133 137 178 181 184 186 190 192 195 197 201 204 207 209 210 210 222
89-103
87 88
7 Fr Ra †
223 226

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To determine the electronic configuration of any element, build the electronic configuration by
following the steps below.

1. The period number shows the shell number.

NOTE: When filling the d orbitals, subtract one from the period number to determine the
correct shell.
2. The block shows the type of orbital.
3. Then add one electron for each element until the orbital, then sub-shell and ultimately the
shell, is full.
4. Record the electronic configuration in the format;

shell number (period), block (orbital), number of electrons (as a superscript)

For example, hydrogen has one electron that is found in the s orbital, in the first shell, hence

1s1 (pronounced “one, s one”)

Helium has two electrons that are found in the s orbital, in the first shell, hence

1s2 (pronounced “one, s two”)

Examples

Number of
Element Electronic configuration Notes
electrons
F 9 1s2 2s2 2p5 Actually (2px2 2py2 2pz1)

P 15 1s2 2s2 2p6 3s2 3p3 Actually (3px1 3py1 3pz1)

Sb 51 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p3 Actually (5px1 5py1 5pz1)

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Task 1.7

1. Fill in the table below.

ATOMIC NUMBER OF
SYMBOL ELECTRONIC CONFIGURATION
NUMBER ELECTRONS

1 H 1 1s1

2 He 2

3 Li 3

4 Be 4

5 B 5

6 C 6

7 N 7

8 O 8

9 F 9

10 Ne 10

11 Na 11

12 Mg 12

13 Al 13

14 Si 14

15 P 15

16 S 16

17 Cl 17

18 Ar 18

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ATOMIC NUMBER OF
SYMBOL ELECTRONIC CONFIGURATION
NUMBER ELECTRONS

19 K 19

20 Ca 20

21 Sc 21

22 Ti 22

23 V 23

24 Cr* 24

25 Mn 25

26 Fe 26

27 Co 27

28 Ni 28

29 Cu * 29

30 Zn 30

31 Ga 31

32 Ge 32

33 As 33

34 Se 34

35 Br 35

36 Kr 36

Cr and Cu are anomalies and have configurations ending 4s1 3d5 and 4s1 3d10 rather than 4s2 3d4
and 4s2 3d9 respectively.

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Noble gas core method of expressing electronic configuration

Rather than writing the full electronic configurations as above, the noble gas core method can be
employed. In this method the electronic configuration is determined by writing the previous noble
gas in square brackets, and then filling orbitals as before. For example, for element number 15,
phosphorus, neon (Ne) is the previous noble gas, and the electrons that follow neon are in the 3s
and 3p sub-shells respectively. In this case, this eliminates the need to write, 1s2 2s2 2p6 for Ne,
therefore shortening the notation, and the noble gas configuration for P becomes; [Ne] 3s2 3p3.

Ions and electronic configuration

Ions are charged particles that are formed from atoms by either the loss or gain of electrons;
positive ions are formed by losing electrons, negative ions are formed by gaining electrons. The
magnitude of the charge (either positive or negative) denotes how many electrons have been lost
or gained. In each case, the electrons are either removed or added to the outermost shell
meaning that when forming positive ions, d block elements lose their outer s electrons before any
d electrons. In order to find the electronic configuration of an ion, simply start with the electronic
configuration of the atom, and either remove or add electrons from there.

Task 1.8

1. Write the electronic configuration of the following using the noble gas core method.

(a) Cu
(b) Co
(c) Ca
(d) C
(e) Ar
(f) Ga

2. Write the electronic configuration of the following simple ions using the noble gas
core method.
(a) F-
(b) Ca2+
(c) S2-
(d) Na+
(e) Al3+

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Electrons in boxes (orbital) notation

So far we have seen how to write electron configurations in the traditional long hand method and
with the shortened noble gas core method. You should be familiar with one other method of
displaying electronic configurations. Consider the examples below.

Carbon, 6 electrons

Nitrogen, 7 electrons

Oxygen, 8 electrons

Fluorine, 9 electrons

Neon, 10 electrons

In these examples, arrows (one up and one down to represent the different ‘spins’) show the
electrons in each orbital and boxes represent the orbitals. As you can, see the three, degenerate,
2p orbitals avoid having electrons paired until it is absolutely necessary (Hund’s rule). In the
notations discussed previously, nitrogen could be represented in one of four ways.

1st way 1s2 2s2 2p3 3rd way [He] 2s2 2p3
2nd way 1s2 2s2 2px1 2py1 2pz1 4th way [He] 2s2 2px1 2py1 2pz1

In the 2nd and 4th ways the three, 2p orbitals are broken down to show the separation of electrons
within the orbitals. The five, degenerate, d orbitals can be represented in a similar way and so, for
example, atoms with electronic structures ending in d5 and d8 respectively would be represented
thus;

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d5 d8

Task 1.9

Using the blanks below complete the electronic configurations for the elements listed.

1s 2s 2p 3s 3p 3d 4s 4p Element

C
1s 2s 2p 3s 3p 3d 4s 4p Element

Ca
1s 2s 2p 3s 3p 3d 4s 4p Element

Ne
1s 2s 2p 3s 3p 3d 4s 4p Element

Cr
1s 2s 2p 3s 3p 3d 4s 4p Element

Ga
1s 2s 2p 3s 3p 3d 4s 4p Element

K
1s 2s 2p 3s 3p 3d 4s 4p Element

Ni
1s 2s 2p 3s 3p 3d 4s 4p Element

N
1s 2s 2p 3s 3p 3d 4s 4p Element

Sc
1s 2s 2p 3s 3p 3d 4s 4p Element

Kr
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TOPIC 1F: Photoelectron Spectroscopy

Using Photoelectron Spectroscopy (PES) as evidence for electronic configuration

Using high-energy ultraviolet or X-ray photons, it is possible for electrons in an atom to absorb
sufficient energy for them to overcome their attraction for the nucleus and to be ejected from the
atom. This is called the photoelectric effect. By analyzing the electrons that are ejected in this
way, PES is used to gather data about the specific electronic structure of an atom. The photons
used to eject electrons have energies given by the relationship between h = Planck's constant
and u = frequency.

E = hu

These energies exceed the ionization energy (IE) (see below), and as a result not only are the
electrons able to overcome the attraction of the nucleus, and are ejected from the atom, but they
also gain kinetic energy (KE). Summarizing the math of that process, E = hu = IE + KE, however
this equation is not important to us in the AP course, but it can serve to show that the analysis of
the kinetic energy of the ejected electrons can be used to produce a PES spectrum that gives
information about the electronic structure of the atom.

Interpreting Photoelectron Spectra

Consider the simulated PES plot for magnesium below, noting CAREFULLY that the x-axis is
plotted ‘backwards’, i.e., with decreasing energy from left to right. This is likely to be the way that
you will see the axis plotted on the AP exam. Also note that the scale of the axis is non-linear.

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The energy associated with each sub-shell is plotted on the x-axis (in units of MJ mol-1), and the
relative number of electrons is plotted on the y-axis – larger (higher) peaks mean a greater
number of electrons. Coulombs law predicts that electrons that are the furthest away from the
nucleus are the easiest to remove, and therefore have the lowest energy. In this example, there
are two electrons with very low energies (0.74), eight with intermediate energies (between 5.31
and 9.07), and two with very large energies (126). This corresponds to an electronic configuration
of 1s2 2s2 2p6 3s2 for Mg.

In an atom of magnesium, the two, 3s electrons in shell 3, furthest from the nucleus (the
outermost electrons are called the valence electrons) are the easiest to remove (0.74); the six, 2p
electrons in shell 2, are next easiest to remove (5.31); the two, 2s electrons also in shell 2, are
the next easiest to remove (9.07); finally the most difficult to remove are the two, 1s electrons in
shell 1 (126), since they are the closest to the nucleus and as such experience the greatest force
of attraction. The innermost electrons, i.e., those other than the valence electrons are called the
core electrons.

The 2s and 2p electrons are similar in terms of their energies because they are in the same shell
as one another, and as such have similar (but not identical) distances from the nucleus.

The ‘reversed x-axis scale’ allows the electronic configuration of Mg to read, left to right, on the
simulated PES plot.

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Task 1.10

1. Sodium has a total of four peaks in its PES spectrum. Energies in MJ mol-1 are 0.50,
3.67, 6.84 and 104 respectively.

(a) Explain the existence of four separate peaks in the spectrum.

(b) Suggest the specific electrons and sub-shells that correspond to each peak.
(c) Which peak would you expect to be the largest (greatest intensity)? Explain your
answer.

2. Neon has an electronic configuration of 1s2 2s2 2p6.

(a) How many unique peaks are expected in neon’s PES spectrum?
(b) Which electrons correspond to the largest energies?
(c) Which peak in the spectrum will have the greatest intensity (be the largest)?
Explain your answer.

3. Which is the first element to exhibit a PES spectrum with five peaks? Explain.

Now consider this, second PES simulation, also for magnesium.

Simulated PES for

Magnesium

126
In this plot, the x-axis is not reversed, and
Relative number of electrons

100 500 rather than one continuous value of

energy, the plot is split into three tiers.

This type of plot will almost certainly not

appear on the AP exam, but you should
10 6 100
appreciate that essentially it is the same
as the plots above, but presented in a
2 2
different manner.
0.74 5.31 9.07

0 10
Energy

Increasing

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PES for mixtures of elements

Now consider the real (not simulated) PES plot for a mixture of multiple elements shown below.
C, N, O and F (highlighted in pink) all have atomic numbers greater than 2, so each 1s peak must
be produced by 2 electrons (they all have electronic configurations that start with 1s2).

http://en.wikipedia.org/wiki/X-ray_photoelectron_spectroscopy

So, why are the 1s peaks not all the same height if they all contain 2 electrons, and if the height
of the peak is proportional to the number of electrons present?

The answer is simple. The elements that are present in the mixture have a wide range of
abundances, with O being the most abundant and F the least, leading to different numbers of
total 1s electrons.

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Very similar (but different) data to that generated in PES could also be presented in tabular form,
with the label ‘ionization energy’ and units of kJ mol-1. (1 eV = 1.602 x 10-22 kJ)

Successive IONIZATION ENERGIES of Mg in kJ mol-1

1st 2nd 3rd 4th 5th 6th 7th 8th 9th 10th 11th 12th
738 1451 7733 10543 13630 18020 21711 25661 31653 35458 169988 189368

The large "jump" in the data between the 2nd and 3rd ionization energies shows that it is relatively
easy to remove the 1st two electrons, but extremely difficult to remove the 3rd (the ionization
energy increases by a multiple of approx. 7). It can be assumed that the 3rd electron is a core
electron, in a new, inner shell, closer to the nucleus, and as such experiences a greater pull from
the nucleus and is therefore more difficult to remove. In other words, it has a higher ionization
energy. This means the first two electrons are the valence electrons and that the element is in
group 2. There is another large "jump" between the 10th and 11th ionization energies. This
indicates the start of the inner (1st) shell, once again closer to the nucleus, and once again
showing a significant increase in ionization energy. These data are consistent with the PES data.

Because ionization energy is associated with only removing the outermost, least tightly held
electron, it is NOT possible to determine the second ionization energy until the first electron has
been removed. As such, the first electron is removed from a neutral atom, and the second (and
subsequent electrons) from positive ions. Because these species are different each time, the 1st,
2nd, 3rd etc. ionization energies are different. However, when considering PES, any electron can
be removed at any time, and in each case the electron will be removed from the same species (a
neutral atom) hence the observed PES energy will be the same for all electrons in any given sub
shell. This is why a single peak is associated with all of the electrons in any given sub-shell, but
multiple ionization energies are associated with electrons within the same sub-shell.

Paramagnetism and diamagnetism

Paramagnetic species are those that are attracted by a magnet and are created when unpaired
electrons are present in an atom. Diamagnetic species are slightly repelled by magnets and occur
when all electrons are paired.

Isoelectronic species

Isoelectronic species have the same electronic configuration. As a result, they must be
distinguished by some other means, for example the number of protons present.

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TOPIC 1G: Periodicity

TOPIC 1H: The Formation of Ions

Periodicity

The chemical and physical properties of the elements and their compounds are very dependent
upon their outermost (valence) electron configurations. When the elements are arranged in the
periodic table in order of ascending atomic number, a regular change in the outermost electronic
configuration is observed. In turn, a regular variation of properties is also observed. This called
the periodic law or periodicity.

Thus, as a period is traversed, certain regular repeatable patterns can be observed which lead to
the ability to make predictions about the unknown properties of elements and their compounds.
This ability to predict the behavior of elements and compounds is crucial in the design of new
materials. For example, if we know that silicon dioxide, SiO2 is a ceramic material, it becomes
reasonable to predict that other group 14 dioxides may be as well*.

Additionally, elements that are in the same group have similar outer electronic configurations
and often behave in a similar manner to one another.

These facts lead to the observation of gradual changes in the physical and chemical properties of
the elements and their compounds when moving about the periodic table. In order to illustrate
these changes we will consider a number of trends and patterns observable in the periodic table.

*It should be noted that whilst several very useful generalizations and patterns can be
discerned, there are also several exceptions and anomalies which need to be appreciated.

GROUP NUMBERS
Modern
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
IUPAC
Headed by
H/Li Be Sc Ti V Cr Mn Fe Co Ni Cu Zn B C N O F He
Element

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The electronic configurations of metals & non-metals and the ions they form

Noble gases (group 18)

All atoms of the noble gases have their outer s and p orbitals filled. We will see later that these
atoms require very large amounts of energy to form ions, so much in fact, that they are difficult to
alter chemically and as such are considered relatively inert (unreactive), and do not tend form
ions or many compounds

Alkali metals (group 1) & Alkaline Earth metals (group 2)

Group 1 atoms have an electronic structure [noble gas] s1. This means that they tend to lose the
s electron when they form an ion, leaving behind an inert noble gas type structure. This explains
why Group 1 elements tend to only form 1+ ions.

Group 2 atoms have an electronic structure [noble gas] s2. This means that they tend to lose the
two s electrons when they form an ion, leaving behind an inert noble gas type structure. This
explains why Group 2 elements tend to only form 2+ ions.

A similar argument can be applied to group 13 atoms and their simple ions.

Groups 16 & 17 (chalcogens & halogens) non-metals

Group 16 atoms have an electronic structure [noble gas] s2 p4. This means that they tend to
gain two, p electrons when they form an ion, in order to reach an inert noble gas type structure
with a charge of 2-. Group 17 atoms have an electronic structure [noble gas] s2 p5. This means
that they tend to gain one, p electron when they from an ion, in order to reach an inert noble gas
type structure with a charge of 1-.

Ionization energy

When metals and non-metals undergo chemical reactions, they are generally trying to achieve a
more stable state. As we have seen above, they do this by either losing electrons (metals) or
gaining electrons (non-metals). In order to make some quantitative sense of this we need to
consider patterns in ionization energy.

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First ionization energy

First ionization energy is formally defined as the energy required to remove one mole of
electrons, from one mole of gaseous atoms, to produce one mole of gaseous ions.

M(g) → M+(g) + e-

The second ionization energy is defined as the energy change accompanying;

M+(g) → M2+(g) + e-

Ionization energies are often measured in units of kJ mol-1. They have positive values indicating
that energy must be “put in” in order to remove electrons. A positive energy change is
described as being endothermic.

The magnitude of the ionization energy is determined by the attraction of the positive nucleus for
the negative electrons that are being removed (essentially Coulomb’s law) and the force of
attraction is dependent upon two factors;

1. The nuclear charge (how many protons are present).

2. The shielding effect of the inner electrons (the extent to which inner electrons protect the
outer electrons from the nuclear charge). Shielding is related to the distance of the electrons
from the nucleus; the greater the distance the shell is from the nuclear charge, the smaller
the attraction.

As a period is traversed from left to right, the first ionization energy of the elements will steadily
increase. This is because the nuclear charge increases (greater positive charge, extra
protons) but the electrons are being removed from the same quantum shell, experiencing no
extra distance from the nucleus, and are therefore held more strongly.

As a group is descended the first ionization energy of the elements will decrease. This is because
although there is again an increase in nuclear charge, the valence electrons are in new shells,
further away from the nucleus, experience more shielding due to the core electrons, and are
therefore held less strongly. Increased distance, rather than the increasing number of protons, is
found to be the more important factor.

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Consider the plot of first ionization energy versus atomic number, below.

The slightly odd behavior of boron & aluminum and oxygen & sulfur can be explained thus;

Boron & aluminum: Elements in group 13 have the valence (outer) electronic configuration s2 p1.
The outer p1 electron is in a p orbital that has a slightly higher energy than the corresponding s
orbital (from which the previous elements first electron is removed) and experiences slightly more
shielding from the full s2 sub-shell in addition to the inner complete shells. As a result, these
elements exhibit slightly lower first ionization energies than would otherwise be expected.

Oxygen & sulfur: Elements in group 16 have the valence (outer) electronic configuration s2 p4.
The electron that is being removed in an ionization process is paired with another in one of the p
orbitals and as a result experiences repulsion. This repulsion means it is more easily lost, and as
a result these elements exhibit slightly lower first ionization energies than would otherwise be
expected.

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Successive ionization energies in a single element

It is possible to remove more than one electron from a single atom and it is found that removing a
subsequent electron is progressively more difficult. This is because once an electron has been
removed, the remaining electrons experience a reduced mutual repulsion. They move slightly
closer to the nucleus and as a result become slightly more attracted to the nucleus. This makes
them more difficult to remove and each subsequent ionization energy increases. In addition, once
one electron has been lost from the atom, subsequent electrons are being removed from a now,
positive species.

As we saw with magnesium above, this effect is even more pronounced when moving to an inner
shell closer to the nucleus, and can be used to make predictions about the group a particular
element is found. Consider the following data for sodium.

Successive IONIZATION ENERGIES of Na in kJ mol-1

1st 2nd 3rd 4th 5th 6th 7th 8th 9th 10th 11th
496 4562 6912 9543 13353 16610 20114 25490 28933 141360 159074

The large "jump" in the data between the 1st and 2nd ionization energies shows that it is relatively
easy to remove the 1st electron but extremely difficult to remove the 2nd (the ionization energy
increases approximately times 10). It can be reasonably assumed that the 2nd electron is in a new
shell, is closer to the nucleus, is more difficult to remove (higher ionization energy) and therefore
the 1st electron was in the valence shell, on its' own, hence group 1. There is another large "jump"
between the 9th and 10th ionization energies. This indicates the start of the inner (1st) shell.

Task 1.11

1. Give a brief but complete explanation of the changes in first ionization energy, as the
following transitions in the periodic table are made.

(a) Passing from magnesium to strontium

(b) Passing from sodium to argon

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2. Consider the following successive ionization energies (kJ mol-1) of elements X & Y.
1st 2nd 3rd 4th 5th 6th
X 513 7298 11814 - - -
Y 737 1450 7732 10540 13360 17995

(a) In which group is X likely to be found?

(b) In which group is Y likely to be found?
(c) There are only three ionization energies listed for X. Suggest a reason.

3. Define the term ‘first ionization energy’ and state the two factors which influence its
magnitude.

4. Consider the following successive ionization energies (kJ mol-1) of element R.

1st 2nd 3rd 4th 5th 6th
737 1450 7732 10540 13360 17995

(a) What is the most likely formula of R's oxide?

(b) Why is the value for the 2nd ionization energy greater than the 1st?

5. Why is there a general increase in ionization energy on passing from Li to Ne?

6. Explain why helium has the largest ionization energy of all the noble gases.

Atomic and ionic size

Variation of atomic size across a period

As a period is traversed from left to right, the atomic size decreases. This is because the nuclear
charge increases (greater positive charge, extra protons) and the subsequent electrons enter the
same shell, experiencing no extra shielding from inner electrons and are therefore attracted
(pulled in) more tightly.

Variation of atomic size down a group

As a group is descended the atomic size increases. This is because that although there is again
an increase in nuclear charge (greater positive charge, extra protons), the valence electrons enter

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new shells, further away from the nucleus. As a result, the atomic size increases since the greater
the number of shells occupied in an atom, the larger the atom.

Cation (positive ion) size

When an atom loses electrons to form a cation, the remaining electrons will experience less
mutual repulsion and as a result they are drawn closer than they were in the in the atom, and the
cation is smaller than the parent atom. It is also true to say that when a cation is formed, an atom
often loses a complete valence shell of electrons which has the effect of decreasing the size of
the cationic species compared to the parent atom.

Anion (negative ion) size

When an atom gains electrons to form an anion the extra electrons that have been added to form
the anion tend to repel one another. This has the effect of slightly enlarging the new anionic
species making the anion larger than the corresponding atom.

Task 1.12

Arrange the following species in order of increasing size.

Ar, K+, Ca2+, S2-, Cl-

Electron affinity

First electron affinity is formally defined as the energy change when one mole of electrons is
added to one mole of gaseous atoms, to produce one mole of gaseous ions.

X(g) + e- → X-(g)

First electron affinity values are exothermic (negative), showing that energy is released when an
electron is added to a gaseous atom.

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For example, the halogens have the following first electron affinities.

Group 17 element First electron affinity in kJ mol-1

F -328
Cl -349
Br -324
I -295

In general, first electron affinities become less negative down a group, since the electrons are
being added to shells that are further from the nucleus, and hence they are pulled toward the
nucleus with a decreasing amount of Coulombic attraction. Fluorine is an anomaly because the
electron is being added to relatively small, compact shell, where there is more crowding of
electrons, and hence there is some repulsion, making the overall net attraction less.

Now consider the group 16 elements and their first electron affinities.

Group 16 element First electron affinity in kJ mol-1

O -142
S -200
Se -195
Te -190

These values have smaller magnitudes than their group 17 counterparts, since the corresponding
number of protons is fewer in group 16 than 17, and as a result, the Coulombic attraction when
adding the electron is less.

The second electron affinity is defined as the energy change accompanying;

X-(g) + e- → X2-(g)

This is where things get much more complicated, for example, consider oxygen. Oxygen’s
second electron affinity is actually a positive, endothermic energy change, since the second
electron has to be forced into a species that is already negative.

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Electronegativity

Electronegativity is defined as the ability of an atom within a covalent bond, to attract electrons to
itself. Non-metal elements in the top right of the periodic table tend to want to attract electrons
more than metal atoms, since in order to achieve full, valence s and p sub-shells, the non-metals
need to acquire electrons. Smaller non-metals tend to have greater attractions for electrons, since
the negative electrons can get closer to the positive nuclei and feel a stronger Coulombic
attraction. Given that the noble gases already have filled s and p sub-shells and are as such have
no need to attract electrons, the most electronegative elements are the halogens, and the most
electronegative of the halogens is fluorine. Metal elements that want to lose electrons in order to
achieve filled s and p valence sub-shells have very low electronegativity’s.

In summary, excluding the noble gases, electronegativity increases across a period, and
decreases down a group.

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Periodic properties of the elements and their compounds

Physical properties within a group

The value of a property tends to change uniformly from top to bottom in a group. For example,
consider some of the physical properties of the elements of group 17, the halogens

Melting point in Boiling point in

State at RT Color
Kelvin Kelvin
Fluorine 53 85 Gas Pale green
Chlorine 172 239 Gas Yellow/green
Bromine 266 332 Liquid Brown/orange
Iodine 387 458 Solid Purple/black

These properties illustrate that there are gradual changes within the group.

Physical properties across a period

Periodic physical properties are less easy to predict with certainty, but sometimes the value of a
property may reach a peak within a period and then reverse the trend. For example, consider the
melting point of the third period elements. Here the melting points rise to a peak at silicon before
falling back to similar smaller values as at the beginning of the period.

Element Melting point in Kelvin

Na 371
Mg 922
Al 933
Si 1683
P 863
S 393
Cl 172
Ar 84

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Chemical properties within a group

For example, consider the reactivity of group 1 and group 2 metals. We have seen how when a
group 1 or a group 2 metal reacts it tends to lose electrons to form a positive ion. We have also
seen how ionization energy decreases down a group. Putting these observations together it
would be reasonable to assume that on passing down groups 1 and 2, that as the ionization
energies decrease, the reactivity would increase. This is found to be true*.

Additionally, it would seem reasonable to assume that when comparing group 1 and group 2
metals in the same period that the group 1 metal would be more reactive. This is because
ionization energy increases across a period and the fact that the group 2 metal must lose two
electrons as opposed to one. Again, this is found to be true*.

The group 1 and 2 metals reaction with water can illustrate this reactivity.

Group 1: 2M(s) + 2H2O(l) → 2MOH(aq) + H2(g)

Group 2: M(s) + 2H2O(l) → M(OH)2(aq) + H2(g)

From the assumptions above, we can predict with some certainty that, for example, potassium
(group 1) would react more vigorously than calcium (group 2) in the same period. This is also
found to be true. We might also predict that beryllium and magnesium (at the top of group 2)
would react less vigorously than barium (further down the group). This is found to be true and
illustrated by the fact that Be and Mg will not react with cold water at all, but Ba shows a vigorous
reaction.

*It should be carefully noted that all of this is complicated by the fact that ionization energy is an
isolated process that involves the removal of an electron from a gaseous species, e.g., Li(g) →
Li+(g) + e-, and that electrode potentials are a similar, but not identical process where aqueous
ions are involved, e.g., Li(s) → Li+(aq) + e-. As such, it is not possible to easily compare ionization
energy with reactivity in this context.

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Chemical properties across a period

For example, consider the acid/base behavior of some oxides in periods 2, 3 and 4.

Sodium oxide. (Basic. Oxide ions pick up H+ from, for example water to produce a base)

Na2O + H2O → 2NaOH

Magnesium oxide & calcium oxide. (Basic. Oxide ions pick up H+ from, for example from acids to
produce a salt and water, or from water to produce a base)

MgO + 2HCl → MgCl2 + H2O

CaO + H2O → Ca(OH)2

Aluminum oxide. (Shows both acidic and basic properties - AMPHOTERIC)

Basic character (react with acid):

Al2O3 + 3H2SO4 → Al2(SO4)3 + 3H2O

Acidic character (react with base):

Al2O3 + 2NaOH + 3H2O → 2NaAl(OH)4

Silicon dioxide. (Insoluble due to its giant macromolecular structure but acts as an acid by
reacting with strong solutions of base under forcing conditions)

SiO2 + 2NaOH → H2O + Na2SiO3

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Other oxides. (Acidic. React with water to produce acids)

N2O5 + H2O → 2HNO3

P2O3 + 3H2O → 2H3PO3

P2O5 + 3H2O → 2H3PO4

(N.B. P2O3 and P2O5 are sometimes written as P4O6 and P4O10 respectively)

SO2 + H2O → H2SO3

SO3 + H2O → H2SO4

Cl2O + H2O → 2HClO

Cl2O7 + H2O → 2HClO4

In summary, the metal elements on the left of the period (for example sodium and magnesium)
form basic oxides. On the right hand side of the period, the oxides of non-metals are acidic. The
point of change in the period occurs around group 13 (for example, aluminum), which can act
amphoterically.

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