Unit 1 Atomic Structure and Properties Notes Only

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Unit 1 - Atomic Structure

& Properties
1.1 Moles and Molar Mass

1.2 Mass Spectroscopy of Elements
1.3 Elemental Composition of Pure Substances
1.4 Composition of Mixtures
1.5 Atomic Structure & Electron Configuration
1.6 Photoelectron Spectroscopy
1.7 Periodic Trends
1.8 Valence Electrons & Ionic Compounds
ISPS Chemistry Jul 2022 page 1 Atomic Structures & Properties
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1.1 Moles & Molar Mass

The Atomic Mass Scale
Scientists of the nineteenth century were aware that atoms of different elements have different
masses and were able to determine formulae from weights of reacting elements.
They found, for example, that each 100.0 g of water contains 11.1 g of hydrogen and 88.9 g of
oxygen. Thus, water contains 88.9 / 11.1 = 8 times as much oxygen, by mass, as hydrogen.
Once scientists understood that water contains two hydrogen atoms for each oxygen atom, H2O,
they concluded that an oxygen atom must have 2 x 8 = 16 times as much mass as a hydrogen
atom.
Hydrogen, the lightest atom, was arbitrarily

assigned a relative mass of 1 (no units).
Atomic masses of other elements were at first
determined relative to this value. Thus, oxygen
was assigned an atomic mass of 16.
The development of more accurate means of determining atomic masses - the Mass Spectrometer
- led to more accurate system based on comparison with the mass of a proton - the Atomic Mass
Unit (amu).

Formula and Molecular Weights
The formula weight of a substance is the sum of the atomic weights of the atoms in the chemical
formula of the substance. Using atomic weights, we find, for example, that the formula weight of
sulfuric acid (H2SO4) is 98.1 amu:*

*For convenience, the atomic weights have been rounded off to one decimal place. In the AP
exam all calculations should be done using the Atomic Weights provided with the Formula Sheet.
Molar Mass, M
The easiest way to 'scale up' to real world quantities is to stick
with the same number but move from measuring mass in amu to
measuring mass in grammes.
This involves using a very large

number that we refer to as 1 mole
(1 mol) and it is the number of
particles needed to convert from amu
to grammes.
Molar Mass = AW or FW in grammes
A packet of an artificial sweetener powder

contains 40.0 mg of saccharin (C7H5NO3S),
which has the structural formula:

Given that saccharin has a molar mass of 183.18 g/mol, how many moles of saccharin molecules
are in a 40.0 mg (0.0400 g) sample of powdered saccharin? How many moles of carbon are in the
same sample?
moles of saccharin, n = m ÷ M, n = 0.0400 / 183.18 = 2.2 x 10-4 mol
7 carbon atoms per molecule, so 7 x 2.2 x 10-4 = 1.5 x 10-3 mol
Saccharin tablets contain 5.5 x 10-4 mol of saccharin. What mass of saccharin is in each tablet?
mass of saccharin, m = n x M, m = 5.5 x 10-4 x 183.18 = 0.10 g = 100 mg
Molar Number - Avogadro's Number
While molar mass provided us with the tool
to move into real world quantities, it
was not long before scientists found ways to
calculate the actual number of particles
required to move from, for example,
1 H2O molecule = 18.0 amu

to 18 g (1mole) = 6.02 x 1023 molecules
There are many ways in which we can think about the quantity we call 1 mole, but the first two
would be:
1 mole is the amount of a substance that contains 6.022 x 1023
elementary entities (atoms, molecules, or other particles)
1 mole is the amount of a substance whose mass in grammes is
numerically equal to its formula weight in atomic mass units
Mole calculations will often require a mathematical understanding of these relationships and the
use of simple formulae linking them.
n = m / M and n = number of particles / NA

1.2 Mass Spectroscopy of Elements

Mass Spectroscopy
Since each proton and each neutron contribute approximately one amu to the mass of an atom,
and each electron contributes far less, the atomic mass of a single atom is approximately equal to
its mass number (a whole number).
Over the years, the atomic mass unit (amu) has been redefined so that, for example, the mass of
a proton is now only approximately 1 amu - it is actually 1.00727 amu. Similarly, the neutron is
actually 1.00866 amu.
More importantly, when protons and neutrons come together to form a nucleus there is an
'energy cost' referred to as the binding energy. As Einstein demonstrated, nuclear energy is linked
to mass, E = mc2, so the actual mass of the nucleus is always less than what would be calculated.
The significance of this is that we cannot always assume that the atomic mass is the same as the
mass number. For example, there are two Chlorine isotopes,
Isotope 1: 17 protons 18 neutrons mass number = 35
17 x 1.00727 18 x 1.00866 atomic mass = 35.2795
E = mc2 atomic mass = 34.9689
Isotope 2: 17 protons 20 neutrons mass number = 37
17 x 1.00727 20 x 1.00866 atomic mass = 37.2968
E = mc2 atomic mass = 36.9659
the differences in these numbers are so small that in 'ordinary' chemistry calculations
there will be very little error in continuing to use the familiar whole numbers.
The mass spectrometer provides us with three important pieces of information:

1. the number of isotopes present, i (2 peaks so 2 isotopes)
2. the atomic mass of each isotope ('35' and '37')
3. the relative amount of each isotope (75.77% and 24.23%)
From this we can calculate the average or relative atomic mass;
average mass = (0.7577 x 34.9689) + (0.2423 x 36.9659)

= 35.4528 amu
molar mass = 35.4528 g
In reality, you are not expected to calculate the average mass. Instead, you are expected to simply
use the spectra to identify the 3 things listed above and also estimate the average mass. So, in the
chlorine example above, it would be enough to recognise that the average would lie closer to 35
than 37, ideally that it would be about half way between 35 and 36.
1.3 Elemental Composition of Pure Substances

Molecular and Empirical Formulae
Even though the atom is the smallest representative sample of an
element, only the noble-gas elements are normally found in nature
as isolated atoms, (monatomic). Several elements are found in nature
in molecular form—two (diatomic) or more of the same type of atom
bound together.
Molecular formulae describe the actual numbers of atoms but they can often be simplified to their
smallest ratio which is called the empirical formula.
Molecular Empirical Mole Mass

Formula Formula Ratio Ratio
H:O H:O
H2O H2O
2:1 1:8
H:O H:O
H2O2 HO
1:1 1 : 16
C:H:O C:H:O
C2H6O2 CH3O
Ethylene 1:3:1 12 : 3 : 16
Glycol, C2H6O2
C:H C:O
C6H6 CH
1:1 12 : 1
Benzene, C6H6
C:H C:H
C2H4 CH2
1:2 6:1
C:H C:H
CH4 CH4
1:4 3:1
N:O C:O
N2O4 NO2
Dinitrogen
1:2 7 : 16
Tetroxide,N2O4

Calculating Empirical Formulae
The key to calculating empirical formulaes is usually to start by determining accurate masses and
then convert to numbers of moles before, finally, converting to mole ratios.
This can often be done using Gravimetric Analysis - accurate measurements of mass.
Example 1, when a 2.50 g sample of copper is heated, it forms 3.13 g of an oxide.
What is its empirical formula?
mass of Cu = 2.50 g
mass of O = 3.13 - 2.50 = 0.63 g
moles of Cu = 2.50 / 63.55 = 0.393 mol
mass of O = 0.63 / 16.00 = 0.394 mol
mole ratio = 0.393 : 0.394 = 1 : 1 = CuO
Example 2, 1.285 g of copper chloride hydrate (CuxCly·nH2O) was heated in a crucible.

After heating and then cooling, the final mass is 1.012 g of copper chloride,
CuxCly.
The CuxCly sample was dissolved in 50 mL of deionized water and 0.2 g of
fine aluminum mesh was added to the beaker.
After reacting and dissolving the excess aluminum, 0.479 g of dried copper
metal is recovered.
mass of Cu = 0.479 g
mass of Cl = 1.012 - 0.479 = 0.533 g
treat H2O like an 'element' mass of H2O = 1.285 - 1.012 = 0.273 g
moles of Cu = 0.479 / 63.55 = 7.53 x 10-3 mol
moles of Cl = 0.533 / 35.45 = 1.50 x 10-2 mol
moles of H2O = 0.273 / 18.01 = 1.51 x 10-2 mol
divide each by smallest Cu Cl H2O
7.53 x 10-3 1.50 x 10-2 1.51 x 10-2
7.53 x 10-3 7.53 x 10-3 7.53 x 10-3
1 : 2 : 2
CuCl2 . 2H2O
Alternatively we can use the results of Compositional Analysis - accurate determination of
percentages. 'Trick' is to assume 100g sample so %'s convert directly to masses, and then proceed
as before.
Example 3, Ascorbic acid (vitamin C) cures scurvy. It is composed of 40.92 % carbon (C),
4.58 % hydrogen (H), and 54.50 % oxygen (O) by mass. Determine its
empirical formula.
mass of C = 40.92 g
mass of H = 4.58 g
mass of O = 54.50 g
moles of C = 40.92 / 12.01 = 3.407 mol
moles of H = 4.58 / 1.008 = 4.54 mol
mass of O = 54.50 / 16.00 = 3.406 mol
divide each by smallest C H O
3.407 4.54 3.406
3.406 3.406 3.406
1 : 1.33 : 1
multiply to make whole numbers 3 4 3 C3 H4 O3
Finally we can use the results of Combustion Analysis - accurate determination of products of
combustion.
mass of sample, CxHyOz mass of CO2 mass of H2O

Calculation for
⇩ ⇩
hydrocarbons
moles of CO2 moles of H2O
⇩ x 1 ⇩x2
moles of O moles of C moles of H ☞ empirical
⇧ ⇩ ⇩
subtract C and H mass of O ☜ mass of C mass of H
from
sample
Calculation for complex organics
Example 4, The combustion of 11.5 g of a liquid produced 22.0 g of CO2 and 13.5 g
of H2O. Determine its empirical formula.
mass of CO2 = 22.0 g ⇨ mass of C = 22.0 x 12.01/44.01 = 6.0 g
mass of H2O = 13.5 g ⇨ mass of H = 13.5 x 2.016/18.02 = 1.51 g
mass of O = 11.5 - (6.0 + 1.51) = 4.0 g
moles of C = 6.0 / 12.01 = 0.50 mol
moles of H = 1.51 / 1.008 = 1.50 mol
mass of O = 4.0 / 16.00 = 0.25 mol
divide each by smallest C H O
0.50 1.50 0.25
0.25 0.25 0.25
2 : 6 : 1 C2 H6 O
Empirical formulae, by themselves, are not

ethanol conclusive proof of the identity of a molecule.
However, when used with other tools like
IR Spectroscopy - identifies functional groups, and
Mass Spectroscopy - identifies mass of molecule
dimethylether
it can be an important first step.
Example 5, Combustion analysis of a hydrocarbon produced: 33.01g CO2 and 13.5g H2O.
Determine its empirical formula.
mass of CO2 = 33.01 g ⇨ moles of CO2 = 33.01/44.01 = 0.75 mol
moles of C = 0.75 x 1 = 0.75 mol
mass of H2O = 13.5 g ⇨ moles of H2O = 13.5/18.02 = 0.75 mol
moles of H = 0.75 x 2 = 1.50 mol
C : H = 0.75 : 1.50 = 1 : 2 CH2 - empirical formula
Mass Spectroscopy reveals molecular mass = 56 amu so C4H8 - molecular formula
IR Spectroscopy reveals presence of C = C bond so a butene rather than cyclobutane

nmr Spectroscopy would narrow down which isomer of butene,
but eventually differences in
physical properties such as
melting points might be needed
for final identification.
Calculating Empirical Formulae for Non Molecular Substances
Nothing really changes except that our 'normal' formula for these
substances is really just an empirical formula, as it represents the
simplest ratio rather than an attempt to measure actual numbers.
So, copper(II) oxide is CuO - representing a 1:1 ratio, whereas
copper(I) oxide is Cu2O - representing a 2:1 ratio.
titanium(IV) oxide
TiO2
copper(II) chloride
CuCl2
Example 6, A sample of the black mineral hematite, an oxide of iron found in many iron
ores, contains 34.97 g of iron and 15.03 g of oxygen. What is the empirical
formula of hematite?
mass of Fe = 34.97 g
mass of O = 15.03 g
moles of Fe = 34.97 / 55.85 = 0.6261 mol
mass of O = 15.03 / 16.00 = 0.9394 mol
divide each by smallest Fe O
0.6261 0.9394
0.6261 0.6261
1 : 1.5
multiply to make whole numbers 2 : 3 Fe2O3 so iron(III) oxide

1.4 Composition of Mixtures
Working with Mixtures

As long as a mixture is homogeneous, we can usually find a way of separating and determining at
least one of the components and determine the purity. For example, the active ingredient in
aspirin. acetyl salicylate, can be extrated from the 'filler' material and analysed to determine the
purity of a tablet of known mass.
Separating Mixtures
To separate the different components in a mixture we
often need to make use of differences in their properties -
particularly solubility.
A mixture of two compounds, one of which is soluble
(CuCl2) while the other is insoluble (CuCl) would simply
require the mixture to be added to water, stirred and then
the insoluble CuCl would be separated by filtration.
The accuracy of this method would depend on the different solubilities but with CuCl2 having a
solubility of 76 g per 100 ml of water and CuCl being 3.91 mg per 100 ml of water, it should be
possible to accurately determine the CuCl as long as the quantity was not too low to begin with.
Determining a mixture of two soluble compounds, such as CuCl2
and NaCl, would need a different approach. Adding a third
chemical such as NaOH would cause Cu to precipitate out
as solid Cu(OH)2. This could be filtered, dried to constant mass
and weighed, allowing the amount of Cu (and hence CuCl2) to be
determined.
Another alternative would be to add a more reactive metal, such
as aluminium, that would cause solid copper to precipitate out
(a displacement reaction). The excess Al could be reacted away with acid, before the copper was
filtered, dried to constant mass and weighed.
An important method of separating the
components of a homogeneous mixture is
distillation, a process that depends on the
different abilities of substances to form
vapours.
The amount of ethanol in an alcoholic drink
or the amount of salt in a sample of sea water
could both be determined using a form of
distillation.
Whatever methods of analysis are used, the
ability to use mole relationships linked to an
understanding of
chemical formulae
and percentages
will be crucial.

1.5 Atomic Structure &

Electron Configuration

Electromagnetic Forces
There is not much that goes on in Chemistry that is not governed by the forces that exist between
charged particles.
The forces of repulsion and attraction are
enormously important in determining the stability
and properties of the atoms that make up
everything in the universe.
The strength of these electromagnetic forces are
determined by two factors:
* the amount of charge , q1 and q2
(positive or negative)
F ∝ q1 x q2
* the distance between charges, r
F ∝ 1 / r1 x r2
This can all be combined in what is

known as Coulombs Law:
F ∝ q1 x q2
r2
Whenever possible, AP Chemistry requires
explanations based on fundamental
mathematical relationships such as Coulombs
Law.

Electron Configurations
Balancing the forces of repulsion and attraction that
can exist between electrons and between electrons
and the positive nucleus required the creation
of a brand new set of maths, Quantum Mechanics -
particularly once it was realised that electrons have
both the properties of charged particles and
wave properties.

One use of Quantum Mechanics is to plot

potential positions for a single electron.
The region in space where there is a greater
than 90% probability of finding the electron
is called an orbital. The simplest shape formed
is spherical and is called an s orbital.
Repulsions between electrons means that a maximum of

2 electrons can occupy the same orbital.
These repulsions also force electrons to move further away
from the nucleus to occupy higher energy levels called
shells.
Shells are represened by a principal quantum number, n, where
n = 1 (1st shell), n = 2 (2nd shell), n = 3 (3rd shell) etc.

There is an s orbital within each shell, so 1s, 2s, 3s etc.

Notice that the absolute position of an orbital
can change.
The 1s orbital, for example, only exists, by
itself, in a Hydrogen (1+) or Helium (2+)
atom.
Coulombs Law, F ∝ (q1 x q2) / r2

explains why the 1s orbital will be closer to
the nucleus in a Helium (2+) compared to a
Hydrogen (1+) atom and, therefore, that a
He atom will be smaller than a H atom.
In larger atoms, the higher charges on
the nuclei pull the 1s orbital even closer.
The first shell is small and only has room for the
1s orbital.
The second shell is larger and there is room for a 2s orbital

and a set of 3 2p orbitals which are dumb-bell shape.

The third shell is even larger and there is room for a 3s orbital, a set of
3p orbitals and a set of 5 3d orbitals which are double dumb-bell shape.
The fourth shell is even larger and there is room for a 4s orbital, a set of 4p orbitals, a set of
4d orbitals and a set of 7 4f orbitals which have complex shapes.
Once electrons start occupying these orbitals, the complex

balance of attractive and repulsive forces means that the
energies of these orbitals are continually shifting, depending on
the occupancy of each orbital.
In particular, there are times when the 4s orbital is at a lower energy
than the 3d orbital.
The filling of orbitals are
governed by a number of rules.
The first of these is called the
Aufbau principle which states
that an electron occupies orbitals
in order from lowest energy to
highest.

The Aufbau principle ensures that

the 1s orbital must be filled before
an electron can be placed in a
higher energy 2s orbital
Our second rule is called the Pauli Exclusion Principle which states that no two electrons can
have the same set of quantum numbers. That is, no two electrons can be in the same state.
Electrons can be in the same shell, same n - 2 in 1st shell

rising to 32 by 4th shell
Electrons can be in the same shape/type of orbital, same l,
2 in an s-orbital rising to 14 in the f-orbital set
Electrons can be in the same type of orbital with same
orientation, same m, both in a px or dxy orbital
So the 2 electrons in a 2px orbital,

for example, would be in the
same shell (2nd), same shaped
orbital (p) with the same
orientation (along x-axis)
so they would have to have
opposite spins.
Orbitals within the same set, e.g. 2p,
are all of equal energy (described
as being degenerate) so the Aufbau
Principle would not differentiate
between them. Our third rule,
Hund's Rule has to be applied.
Hund's Rule of Maximum Multiplicity states that every orbital in a sublevel is singly occupied
before any orbital is doubly occupied, and that all of the electrons in singly occupied orbitals have
the same spin (to maximize total spin).
Once each orbital is occupied, then
the Pauli Exclusion Principle ensures
that the second electron has the
opposite spin to the original single
electrons.
We have two main methods for describing

the electron configuration of an atom. The
first method is referred to as standard
notation and describes in terms of shells
and sub-shells.
A variation is to describe the inner shells

by reference to the equivalent noble gas and
then describe the outer shell in detail.
I: 1s22s22p63s23p64s23d104p65s24d105p5
becomes I: [Kr]5s24d105p5
The other method is often referred to as 'electrons in boxes'

and has the advantage of being able to show spins.
Both methods, however, will require you to remember that the
overlapping of shells means that, for example, the 4s orbital is
filled before the 3d orbitals due to the fact that the 4s orbital is at
a lower energy and, by the Aufbau Principle, must be filled before the higher energy 3d orbitals.
However, once filled, the 4s orbital is higher than the 3d so, when forming ions, electrons are lost
from the 4s orbital first before electrons are lost from 3d orbitals.
Effective Nuclear Charge
Coulombs Law, F ∝ (q1 x q2) / r2 describes how the force of attraction will be affected
by the both the charge on an electron (q1) and the
charge on the nucleus (q2).
The charge on the nucleus can be calculated
on the basis of the number of protons, so a
sodium atom should have a charge of 11+.
However, the outer electron (the valence
electron) will actually experience a
significantly smaller charge.
The 10 electrons in the inner orbitals
(the core electrons) will be shielding the outer
electron so that it effectively experiences an overall charge closer to 11 - 10 = 1+.
Atoms in the same group would have the same effective nuclear charge ......
Li: 3 - 2 = 1+ Be: 4 - 2 = 2+ O: 8 - 2 = 6+ F: 9 - 2 = 7+
Na: 11 - 10 = 1+ Mg: 12 - 10 = 2+ S: 16 - 10 = 6+ Cl: 17 - 10 = 7+
K: 19 - 18 = 1+ Ca: 20 - 18 = 2+ Se: 34 - 28 = 6+ Br: 35 - 28 = 7+
..... whilst the effective nuclear charge increases as you go across a row in the Periodic Table.
In reality, the maths is more
complicated, so effective nuclear
charges are rarely exact whole numbers
but the same relationships apply.
In reality the effective nuclear charge
increases slightly as you go down a
Group, but this has a minimal effect
compared with the extra distance, r ,
caused by the extra electron shell.
Atomic radius decreases as you go across a Period because effective nuclear charge
increases so outer shell is pulled closer - F ∝ (q1 x q2) / r2 and q is increasing
Atomic radius increases as you go down a Group because an extra shell is being
added so pull weakens - F ∝ (q1 x q2) / r2 and r is increasing

Ionisation energy decreases as you go down a

Group because an extra shell is being added so
attraction weakens - F ∝ (q1 x q2) / r2 and r is
increasing - so it is easier to remove an electron.
Ionisation energy increases as you go across a
Period because effective nuclear charge increases
so outer shell is attracted more strongly and pulled
closer - F ∝ (q1 x q2) / r2 and q is increasing - so it
is harder to remove an electron.
Another very important property that can be explained using Coulomb's Law is electronegativity.
Electronegativity measures an atoms ability to attract the electrons in a shared pair - in a covalent
bond, eg. P—H in PH3 . If one atom is sufficiently more electronegative than the other then the
bond will be polar covalent, eg. O𝛿-—H𝛿+ in H2O . If one atom is much more electronegative than
the other then the bond will become ionic, eg. Na+ Cl—.
Electronegativity decreases as you go down a Group because an extra shell is being added so
attraction weakens - F ∝ (q1 x q2) / r2 and r is increasing - so it is harder to attract an electron.
Electronegativity increases as you go across a Period because effective nuclear charge increases so
shared electrons are attracted more strongly - F ∝ (q1 x q2) / r2 and q is increasing
Magnetism
The way a substance behaves in a magnetic field can in some cases provide insight into the
arrangements of its electrons. Molecules with one or more unpaired electrons are attracted to a
magnetic field. The more unpaired electrons in a species, the stronger the attractive force. This type
of magnetic behavior is called paramagnetism.
Substances with no unpaired electrons are weakly
repelled by a magnetic field. This property is called
diamagnetism. The Pauli Exclusion Principle ensures
that paired electrons have opposite spins so their magnetic
properties cancel out.
Most magnetic properties are

shown by transition metals as
Hund's Rule of Maximum
Multiplicity ensures that up to
5d orbitals can be occupied by
single electrons.
The effects are small but can be measured by

balancing a tube containing a sample of your
substance against masses that are sitting on a
very accurate (at least 4 dp) balance.
Switching on the electromagnets will have no effect on a
diamagnetic substance. A paramagnetic substance, however, will
be pulled down by the magnetic field.
The mass being recorded by the balance will decrease slightly.
We would detect this with a tube filled with an Fe2+ compound,
and even more with an Fe3+ compound
The effect is weak because the iron ions will start off with
all possible orientations. Once in a magnetic field they will
try and line up with the magnetic field but only a small
number will succeed.
The effect can be strengthened by helping the particles line up. This
can best be achieved with iron atoms. Repeated application of a
magnetic field (and heat) will leave the iron atoms lined up and a
permanent magnetic effect can be produced - ferromagnetism.
1.6 Photoelectron Spectroscopy
Photoelectron spectroscopy (PES)

Photoelectron spectroscopy (PES) was formerly known as X-ray electron spectroscopy or XES. It
involves the use of a device that focuses a monochromatic beam of X-rays at a solid sample.
The process is similar to the situation that would exist if you needed to kick some balls out of
some ditches. To help you, you have a highly trained kicker who can consistently kick a ball with
exactly 100 J of energy.
One ball emerges with 70J of Kinetic Energy
so we know that it required 30J to escape.
from the ditch - escape energy = 30J
Two balls emerge with only 55J of KE, so we
know that it required 45J to escape - they
were in a deeper ditch.
In photoelectron spectroscopy, electrons are 'kicked' by X-rays
of equal energy. Some electrons (from higher orbitals) emerge
with more KE while others (from lower orbitals) needed more of
the energy to simply escape so they emerge with less KE.
It is the 'escape energy' or ionisation energy that is recorded.
This process is virtually identical to the
one used to determine the first
ionization energy of an atom except that
we are only able to remove one electron
from the valence shell.
Using very high energy UV or X-ray
photons we are able to remove core
electrons as well and build up a complete
'picture' of the electronic configuration.
High ionisation/binding/escape energies
correspond to orbitals closer to the
nucleus.
The height of a peak corresponds to the number of electrons present in an orbital set:
s-orbitals - 1 - 2 electrons
p-orbitals - 1 - 6 electrons
d-orbitals - 1 - 10 electons
The highest binding energy (on left) has
to belong to the orbital closest to the
nucleus so 1s2
This also establishes the height that is
equivalent to 2 electrons.
Moving left to right-
The next signal has to be for the 2s orbital and the height confirms 2 electrons so - 2s2
The next signal has to be for the 2p orbitals and the height confirms 6 electrons so - 2p6
The next signal has to be for the 3s orbital and the height confirms 2 electrons so - 3s2
The final signal has to be for the 3p orbitals and the height confirms 3 electrons so - 3p3
So complete electron configuration - 1s2 2s2 2p6 3s2 3p3 15 electrons in total so Phosphorus
In this example, we again start with the

highest binding energy peak on the left
which will always be the 1s orbital.
If there are electrons further out then
the 1s must be filled so 1s2.
The next peak must be 2s but height
tells us 2s1 - 1s2 2s1 - Lithium
Explaining Relationships
Coulomb's Law can again be used to explain some aspects of Photoelectron Spectroscopy.
F ∝ (q1 x q2) / r2
Both hydrogen, 1s1 , and helium, 1s2 , have very similar electron configurations but you should
notice, and be able to explain, the fact that it takes slightly more energy to remove from helium
than from hydrogen.
Whilst you might predict that the extra repulsions caused by having two electrons in the 1s
orbital would cause the orbital to expand further out from the nucleus, increasing r and,
therefore decreasing F, the opposite is happening. F must be increasing as more energy is needed
to remove the electrons.
So it must be due to the fact that the Helium nucleus is 2+ whereas the Hydrogen is only 1+.
Increasing q will cause F to increase and will explain why more energy is needed to remove the
electrons.
With lithium and beryllium, we now have both 1s and 2s orbitals. The 2s orbitals are further from
the nucleus so the increased r means that F has decreased, making it easier to remove 2s electrons
than 1s electrons.
Notice, however, that each time the energy needed to remove from the 1s orbital is increasing. As
the nuclear charge increases to 3+ and then 4+. Increasing q will cause F to increase and will
explain why more energy is needed to remove the electrons.
With boron, we now have 2p orbitals. The

2p orbitals are further from the nucleus so
the increased r means that F has decreased,
making it easier to remove 2p electrons than
2s and 1s electrons.

1.7 Periodic Trends

Periodic Trends
Coulomb's Law can again be used to explain some aspects of Periodic Trends.
F ∝ (q1 x q2) / r2
Ionisation Energies:- The overall general trends are best explained using Coulombs Law.
As you go down a Group - Li - Fr or He - Rn - the ionisation energy decreases.
With each extra shell added, the distance r increases, so F decreases meaning that
it will become easier to remove an electron so ionisation energy decreases.
(Though charge on nucleus is increasing, this is cancelled out by the extra screening,
so we consider atoms in the same group to have similar effective nuclear charge.)
As you go across a Period - Li - Ne or Na - Ar - the ionisation energy increases.

With each extra proton added, the effective nuclear charge q increases, so F increases
meaning that it will become harder to remove an electron so ionisation energy
increases.
However, the increase is not regular and we need to consider our shell model as well
as Coulomb's law to fully explain the trend

The increase from Li to Be is
expected and is explained by
increase in effective nuclear
charge.
The decrease from Be to B is
not expected, but is explained by
the fact that 2p orbitals are
further out and increase in r
must be having a bigger effect
than the increase in effective
nuclear charge.
The increase from B to C is
expected and is explained by
increase in effective nuclear
charge.
The decrease from N to O is not expected and cannot be fully explained simply using Coulomb's
Law. The effective nuclear charge, q has increased and we are in the same 2p orbitals so r should
be unchanged.
Instead, we explain the reduction in ionisation energy by assuming that the extra repulsions
caused by the first pairing of electrons is enough to counteract the increase in effective nuclear
charge.
The increase from O to F is expected and is explained by increase in effective nuclear charge.
Atomic & Ionic Radii:-

And again, the general trends are best
explained using Coulombs Law.
Positive ions (cations) are always
smaller than the original atom as
the remaining electrons experience a
higher relative charge, q increases so
F increases which pulls the remaining
electrons closer so the radius
decreases.
With simple ions, all of the electrons
in the outer shell are lost so the ion has
one shell less and will much smaller as
a result.
Na 1s2 2s2 2p6 3s1 ⇨ Na+ 1s2 2s2 2p6
Negative ions (anions) are always

larger than the original atom as
the increased number of electrons
experience a lower relative charge,
q decreases so F decreases which
allows the remaining electrons to move
further away so the radius increases.
O 1s2 2s2 2p6 ⇨ O2- 1s2 2s2 2p8

This time there is no change in the
number of electron shells, just
the same number of protons having to
attract more electrons.
As you go down a Group - for both atoms and ions - the radius increases.
With each extra shell added, the distance r increases.
As you go across a Period - atoms - the radius decreases.

meaning that it the outer shell will be pulled closer to nucleus so radius decreases.
As you go across a Period - positive ions only - the radius decreases.

As you go across a Period - negative ions only - the radius decreases.

Electron Affinities:-
The electron affinity (EA) of an element is the energy change that
occurs when an electron is added to a gaseous atom to give an anion.
E(g) + e −→ E−(g)
While ionisation energies and electronegativities have quite definite trends which can, therefore,
be 'easily' explained, electron affinities are harder to describe and explain.
In general, elements with the most negative electron affinities (the highest affinity for an added
electron) are those with the smallest size and highest ionization energies and are located in the
upper right corner of the periodic table.
Taking the halogens for example, the increasing negative value from At to Cl can be explained by
the fact that the electron gained is entering a shell that is closer to the nucleus and so would be
attracted more strongly.
With Fluorine, however, the electron is entering the 2nd shell, which is significantly smaller than
the 3rd shell (for Chlorine), and the extra repulsions mean that, despite being closer to the
nucleus, the electron affinity is less negative for fluorine then chlorine.
Electronegativity:-
measures an atoms ability to attract the electrons in a shared pair
- in a covalent bond
Electronegativity decreases as you go
down a Group because an extra shell is
being added so attraction weakens -
F ∝ (q1 x q2) / r2 and r is increasing -
so it is harder to attract an electron.
Electronegativity increases as you go
across a Period because effective nuclear
charge increases so shared electrons are
attracted more strongly -
F ∝ (q1 x q2) / r2 and q is increasing
The properties discussed in this section (size of atoms and ions, effective nuclear charge,
ionisation energies, and electron affinities) are central to understanding chemical reactivity.
For example, because fluorine has an energetically favorable EA and a large energy barrier to
ionisation (IE), it is much easier to form fluorine anions (F—) than cations (F+).
Metallic properties depend on having electrons that can be removed easily. Similarly for oxidising
& reducing agents.
1.8 Valence Electrons & Ionic Compounds
Bonding & Energy

Regardless of the nature of the bond being formed, the driving force is always the extra stability
that comes from moving to a lower energy level.
Forces of attraction (F ∝ (q1 x q2) / r2) between shared electrons and positive nuclei or between
positive and negative ions will be balanced by the forces of repulsion (F ∝ (q1 x q2) / r2) between
electrons and between nuclei or between positive ions or between negative ions.
Type of Bond
All of the properties discussed previously (size of atoms and ions, effective nuclear charge,
ionisation energies, electronegativity and electron affinities) can play a part in determining the
type of bond that forms.
The most useful property, however, is probably
electronegativity.
As atoms approach and overlap it will be
differences in their ability to attract electrons
that will largely determine the type of bond that
forms.
However, this is not 'black & white' - bonding is a
continuum with many 'shades of grey'
For example, aluminium forms analogous compounds with the halogens - AlF3 , AlCl3 , AlBr3 etc.
Al F Al Cl Al Br Al I
electronegativity 1.6 3.98 1.6 3.16 1.6 2.96 1.6 2.66
∆EN = 2.38 = 1.56 = 1.36 = 1.06
prediction ionic polar covalent polar covalent polar covalent
MPt (°C) 1290 193 98 188
Structure network molecular molecular molecular
Empirical AlF3 AlCl3 AlBr3 AlI3
Formula
Molecular Formula Al2Cl6 Al2Br6 Al2I6

So, though a compound between a metal and a non-metal, AlCl3 has a low melting point and a
molecular structure which is typical of a covalent compound. However, when molten, AlCl3 is a
good electrolyte which means that it does form Al3+ and Cl— ions and can also be considered an
ionic compound.
Normally, it is safe enough to assume that atoms near the edges of the Periodic Table will behave
'normally' but properties can be a bit more mixed towards the middle.
Many atoms gain or lose electrons to become

more stable. Having the the same number of
electrons as the noble gas closest to them in
the periodic table can be part of that stability.
Same But Different - Elements in the same

Group will have many similar properties,
such as same charge on ion, same effective
charge (Zeff or q ) and, same formulae.
However, as number of shells / distance
from nucleus (r) increases, expect other
properties to be changing:-
atomic radius (⇡), electronegativity (⇣)
ionisation energy (⇣), ionic character (⇡)
Same But Different - Elements in the same Period/Row have the same number of shells / similar
distance from nucleus (r).
However, as effective charge (Zeff or q ) increases, expect other properties to be changing:-
atomic radius (⇣) electronegativity (⇡) ionisation energy (⇡)

Unit 1 Atomic Structure and Properties Notes Only

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Unit 1 - Atomic Structure

1.1 Moles and Molar Mass

ISPS Chemistry Jul 2022 page 2 Atomic Structures & Properties

BY: Credit must be given to me, the creator.

ISPS Chemistry Jul 2022 page 3 Atomic Structures & Properties

1.1 Moles & Molar Mass

ISPS Chemistry Jul 2022 page 4 Atomic Structures & Properties

Hydrogen, the lightest atom, was arbitrarily

ISPS Chemistry Jul 2022 page 5 Atomic Structures & Properties

This involves using a very large

Molar Mass = AW or FW in grammes

A packet of an artificial sweetener powder

1 H2O molecule = 18.0 amu

n = m / M and n = number of particles / NA

ISPS Chemistry Jul 2022 page 7 Atomic Structures & Properties

1.2 Mass Spectroscopy of Elements

ISPS Chemistry Jul 2022 page 8 Atomic Structures & Properties

The mass spectrometer provides us with three important pieces of information:

average mass = (0.7577 x 34.9689) + (0.2423 x 36.9659)

1.3 Elemental Composition of Pure Substances

ISPS Chemistry Jul 2022 page 10 Atomic Structures & Properties

Molecular Empirical Mole Mass

ISPS Chemistry Jul 2022 page 11 Atomic Structures & Properties

Example 2, 1.285 g of copper chloride hydrate (CuxCly·nH2O) was heated in a crucible.

mass of sample, CxHyOz mass of CO2 mass of H2O

Empirical formulae, by themselves, are not

C : H = 0.75 : 1.50 = 1 : 2 CH2 - empirical formula

Mass Spectroscopy reveals molecular mass = 56 amu so C4H8 - molecular formula

IR Spectroscopy reveals presence of C = C bond so a butene rather than cyclobutane

ISPS Chemistry Jul 2022 page 15 Atomic Structures & Properties

1.4 Composition of Mixtures

Working with Mixtures

ISPS Chemistry Jul 2022 page 17 Atomic Structures & Properties

1.5 Atomic Structure &

ISPS Chemistry Jul 2022 page 18 Atomic Structures & Properties

This can all be combined in what is

One use of Quantum Mechanics is to plot

Repulsions between electrons means that a maximum of

There is an s orbital within each shell, so 1s, 2s, 3s etc.

Coulombs Law, F ∝ (q1 x q2) / r2

The second shell is larger and there is room for a 2s orbital

Once electrons start occupying these orbitals, the complex

ISPS Chemistry Jul 2022 page 21 Atomic Structures & Properties

The Aufbau principle ensures that

Electrons can be in the same shell, same n - 2 in 1st shell

So the 2 electrons in a 2px orbital,

We have two main methods for describing

A variation is to describe the inner shells

The other method is often referred to as 'electrons in boxes'

ISPS Chemistry Jul 2022 page 24 Atomic Structures & Properties

Ionisation energy decreases as you go down a

Most magnetic properties are

The effects are small but can be measured by

1.6 Photoelectron Spectroscopy

Photoelectron spectroscopy (PES)

In this example, we again start with the

With boron, we now have 2p orbitals. The

ISPS Chemistry Jul 2022 page 29 Atomic Structures & Properties

1.7 Periodic Trends

ISPS Chemistry Jul 2022 page 30 Atomic Structures & Properties

As you go across a Period - Li - Ne or Na - Ar - the ionisation energy increases.

ISPS Chemistry Jul 2022 page 31 Atomic Structures & Properties