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Atomic Structure (Physical chemistry)

Monday, 2 September 2024 21:10

Structure of an Atom
• All matter is composed of atoms, which are the smallest parts of an element that can take place in chemical reactions
• Atoms are mostly made up of empty space around a very small, dense nucleus that contains protons and neutrons
• The nucleus has an overall positive charge
○ The protons have a positive charge and the neutrons have a neutral charge
• Negatively charged electrons are found in orbitals in the empty space around the nucleus

Subatomic Particles
• The protons, neutrons and electrons that an atom is made up of are called subatomic particles
• so small that it is not possible to measure their masses and charges using conventional units (such as grams or coulombs)
• Instead, their masses and charges are compared to each other, and so are called ‘relative atomic masses’ and ‘relative atomic charges’
• These are not actual charges and masses but charges and masses of particles relative to each other
○ Protons and neutrons have a very similar mass, so each is assigned a relative mass of 1
○ Electrons are 1836 times smaller than a proton and neutron, and so their mass is often described as being negligible
• The relative mass and charge of the subatomic particles are:
Relative mass & charge of subatomic particles table

Exam Tip
You can see from the table how the relative mass of an electron is almost negligibleThe charge of a single electron is -1.602 x 10-19 coulombs, whereas the charge of a proton is +1.602 x 10-19 coulombs. So,
relative to each other, their charges are -1 and +1 respectively

Relative atomic mass: 1.66 x 10 -27 kg

Atoms: Key Terms
• The atomic number (or proton number) is the number of protons in the nucleus of an atom and has the symbol Z
○ The atomic number is also equal to the number of electrons present in a neutral atom of an element
○ E.g. the atomic number of lithium is 3, meaning that a neutral lithium atom has 3 protons and therefore, also has 3 electrons
• The mass number (or nucleon number) is the total number of protons + neutrons in the nucleus of an atom, and has the symbol A
• The number of neutrons can be calculated by:
Number of neutrons = mass number - atomic number
○ Protons and neutrons are also called nucleons, because they are found in the nucleus
Exam Tip

The mass (nucleon) and atomic (proton) number are given for each element in the Periodic Table

Notes Page 1
Mass & Charge Distribution
• The mass of an atom is concentrated in the nucleus, because the nucleus contains the heaviest subatomic particles (the neutrons and protons)
○ The mass of the electron is negligible
• The nucleus is also positively charged due to the protons
• Electrons orbit the nucleus of the atom, contributing very little to its overall mass, bu t creating a ‘cloud’ of negative charge
• The electrostatic attraction between the positive nucleus and negatively charged electrons orbiting around it is what holds an atom together

The mass of the atom is concentrated in the positively charged nucleus which is attracted to the negatively charged electrons orbiting around it

Behaviour of Subatomic Particles in an Electric Field

• Protons, neutrons and electrons behave differently when they move at th e same velocity in an electric field
• When a beam of electrons is fired past the electrically charged plates, the electrons are deflected very easily away from the negative plate towards the positive plate
○ This proves that the electrons are negatively charged; like charges repel each other
○ It also shows that electrons have a very small mass, as they are easily deflected
• A beam of protons is deflected away from the positive plate and towards the negative plate
○ This proves that the proton is positively charged
○ As protons are deflected less than electrons, this also shows that protons are heavier than electrons
• A beam of neutrons is not deflected at all
○ Which proves that the particle is neutral in character; it is not attracted to, or repelled by, the negative or positive plate

The lighter electrons undergo much more deflection than the protons

Determining the Subatomic Structure of Atoms & Ions

• An atom is neutral and has no overall charge
• Ions on the other hand are formed when atoms either gain or lose electrons, causing them to become charged
• The number of subatomic particles in atoms and ions can be determined given their atomic (proton) number, mass (nucleon) number and charge
Protons
• The atomic number of an atom and ion determines which element it is
• Therefore, all atoms and ions of the same element have the same number of protons (atomic number) in the nucleus
○ E.g. lithium has an atomic number of 3 (three protons) whereas beryllium has atomic number of 4 (4 protons)
• The number of protons equals the atomic (proton) number
• The number of protons of an unknown element can be calculated by using its mass number and number of neutrons:
Mass number = number of protons + number of neutrons
Number of protons = mass number - number of neutrons

Worked example: Determine the number of protons

Atomic & Ionic Radius

Atomic radius
• The atomic radius of an element is a measure of the size of an atom
How to measure?
• It is half the distance between the two nuclei of two covalently bonded atoms of the same type

Notes Page 2
 • It is half the distance between the two nuclei of two covalently bonded atoms of the same type

The atomic radius of a hydrogen atom is determined by halving the distance between the nuclei of two hydrogen atoms covalentl y bonded

How is it useful?
• Atomic radii show predictable patterns across the Periodic Table
○ They generally decrease across each Period
○ They generally increase down each Group

• These trends can be explained by the electron shell theory

○ Atomic radii decrease as you move across a Period as the atomic number increases (increased positive nuclear charge) but at the same time extra
electrons are added to the same principal quantum shell
○ The larger the nuclear charge, the greater the pull of the nuclei on the electrons which results in smaller atoms
○ Atomic radii increase moving down a Group as there is an increased number of shells going down the Group
○ The electrons in the inner shells repel the electrons in the outermost shells, shielding them from the positive nuclear charge
○ This weakens the pull of the nuclei on the electrons resulting in larger atoms

Trends in the atomic radii across a period and down a group

• The diagram shows that the atomic radius increases sharply between the noble gas at the end of each period and the alkali metal at the beginning of the
next period
• This is because the alkali metals at the beginning of the next period have one extra principal quantum shell
○ This increases shielding of the outermost electrons and therefore increases the atomic radius

Ionic radius
• The ionic radius of an element is a measure of the size of an ion

• Ionic radii show predictable patterns

○ Ionic radii increase with increasing negative charge
○ Ionic radii decrease with increasing positive charge

• These trends can also be explained by the electron shell theory

○ Ions with negative charges are formed by atoms accepting extra electrons while the nuclear charge remains the same
○ The outermost electrons are further away from the positively charged nucleus and are therefore held only weakly to the nucleus which increases the
ionic radius
○ The greater the negative charge, the larger the ionic radius
○ Positively charged ions are formed by atoms losing electrons
○ The nuclear charge remains the same but there are now fewer electrons which undergo a greater electrostatic force of attraction to the nucleus
which decreases the ionic radius
○ The greater the positive charger, the smaller the ionic radius

Notes Page 3
 ○

Trends in the ionic radii across a period and down a group

Isotopes
• Isotopes are atoms of the same element that contain the same number of protons and electrons but a different number of neutrons
• The symbol for an isotope is the chemical symbol (or word) followed by a dash and then the mass number
○ Eg. carbon-12 and carbon-14 are isotopes of carbon containing 6 and 8 neutrons respectively

The atomic structure and symbols of the three isotopes of hydrogen

Chemical Properties Physical properties

• Isotopes of the same element display the same chemical • The only difference between isotopes is the number of neutrons
characteristics • Since these are neutral subatomic particles, they only add mass to the
• This is because they have the same number of electrons in atom
their outer shells • As a result of this, isotopes have different physical properties such as
• Electrons take part in chemical reactions and therefore small differences in their mass and density
determine the chemistry of an atom

Basic Electronic Structure

• The arrangement of electrons in an atom is called the electronic configuration

Shells (K, L, M)
• Electrons are arranged around the nucleus in principal energy levels or principal quantum
shells
• Principal quantum numbers (n) are used to number the energy levels or quantum shells

○ The lower the principal quantum number, the closer the shell is to the nucleus
○ The higher the principal quantum number, the higher the energy of the shell
• Each principal quantum number has a fixed number of electrons it can hold

Notes Page 4
 • Each principal quantum number has a fixed number of electrons it can hold
○ n = 1 : up to 2 electrons
○ n = 2 : up to 8 electrons
○ n = 3 : up to 18 electrons
○ n = 4 : up to 32 electrons

Electrons are arranged in principal quantum shells, which are numbered by principal quantum
numbers

Sub-shells
• The principal quantum shells are split into sub-shells which are given the letters s, p and d (Elements with
more than 57 electrons also have an f shell)
○ The energy of the electrons in the sub-shells increases in the order s < p < d
• The order of sub-shells appear to overlap for the higher principal quantum shells as seen in the diagram
below:

At principal quantum shell n = 3, the energy levels of the sub-shells start to overlap

Ground state
• The ground state is the most stable electronic configuration of an atom which has the lowest amount of
energy
• This is achieved by filling the sub-shells with the lowest energy first (1s)
• The order of the sub-shells in terms of increasing energy does not follow a regular pattern at n = 3 and higher

Aufbau Principle
The order of filling electrons in the subshells based on the energy of the
subshell.

Notes Page 5
 • The transition metals fill the 4s sub-shell before the 3d sub-shell
but lose electrons from the 4s first and not from the 3d sub-shell
○ Remember: The 4s sub-shell is lower in energy

Orbitals
• Sub-shells contain one or more atomic orbitals
• Orbitals exist at specific energy levels and electrons can only be found at these specific levels, not in
between them
○ Each atomic orbital can be occupied by a maximum of two electrons

Subshells s p d f
One orbital Three orbitals (px, py, pz) Five orbitals Seven orbitals
1x2 = total of 2 electrons 3x2 = total of 6 electrons 5x2 = total of 10 electrons 7x2 = total of 14 electrons

• In the ground state, orbitals in the same subshell have the same energy and are said to be degenerate, so the
energy of a px orbital is the same as a py orbital

Energy of the Sub-shells Summary

• The principal quantum shells increase in energy with increasing principal quantum
number
○ E.g. n = 4 is higher in energy than n = 2
• The sub-shells increase in energy as follows: s ＜ p ＜ d ＜ f
○ The only exception to these rules is the 3d orbital which has slightly higher energy
than the 4s orbital
○ Because of this, the 4s orbital is filled before the 3d orbital
• All the orbitals in the same sub-shell have the same energy and are said to be degenerate
○ E.g. px, py and pz are all equal in energy

Azimuthal quantum number

- Describes the shape of the orbital
- Denoted by the symbol "l"
- The values of l ranges from 0 to n-1

How to calculate energy level?

n+l

Shapes of s and p Orbitals

S orbital P orbital
Spherical in shape Dumbbell-shaped
• The p orbitals occupy the x, y and z-axis and point at

Notes Page 6
 Shapes of s and p Orbitals
S orbital P orbital
Spherical in shape Dumbbell-shaped
• The p orbitals occupy the x, y and z-axis and point at
right angles to each other so are
oriented perpendicular to one another
size of the s orbitals increases with increasing shell number • The lobes of the p orbitals become larger and longer with
• E.g. the s orbital of the third quantum shell (n = 3) is increasing shell number
bigger than the s orbital of the first quantum shell (n = 1)
Every shell has three p orbitals except for the first one (n=1)

• The orbitals have specific 3-D shapes

Representation of orbitals (the dot represents the nucleus of the atom)

showing (a) spherical s orbitals and (b) p orbitals containing ‘lobes’ along the x, y
and z axis

Describing Electronic Configurations

• The electron configuration gives information about the number of electrons in each shell, sub-shell and orbital of an atom
• The sub-shells are filled in order of increasing energy

Subshell configuration (1s2 notation)

All the electrons present within an atom, which is distributed in the particular subshell, are shown precisely.
Also indicates the probable region of finding electrons, relative energies and the position of electrons in the atomic space.

Notes Page 7
Four quantum numbers

Transition Metal Rules

○ Fill 4s before 3d (because it's lower energy)
○ Remove from 4s before 3d in ions (still the outermost
shell)
Exceptions
• Chromium and copper have the following electron configurations, which
are different to what you may expect:

○ Cr is [Ar] 3d5 4s1 not [Ar] 3d4 4s2

○ Cu is [Ar] 3d10 4s1 not [Ar] 3d9 4s2
• because they offer a more stable configuration. With chromium, one 4s electron moves to
the 3d orbital, because a half-filled d shell (5 electrons) is more stable than a partially
filled shell. Similarly for copper, one 4s electron moves to the 3d orbital to completely fill it
as a filled d subshell (10 electrons) is more stable than a partially filled one, even if it
results in a partially filled 4s subshell.
• This is only possible with outer most shell and next s hell closest to it.

Shorten electronic configuration

Electronic configuration of ions

Notes Page 8
 • The Periodic Table is split up into four main blocks depending on their electronic configuration:
○ s block elements
▪ Have their valence electron(s) in an s orbital
○ p block elements
▪ Have their valence electron(s) in a p orbital
○ d block elements
▪ Have their valence electron(s) in a d orbital
○ f block elements
▪ Have their valence electron(s) in an f orbital

• Explaining electronic Configurations

Electron spin
• Electrons can be imagined as small spinning charges which rotate around their own axis in either a clockwise or anticlockwise
direction
• The spin of the electron is represented by its direction

Spin-pair repulsion
• Electrons with similar spin repel each other which is also called spin-pair repulsion

• Electrons will therefore occupy separate orbitals in the same sub-shell to minimise this repulsion and have their spin in the same
direction

When there are three electrons in a p sub-shell, one electron will go into each p x, py and pz orbital

• Electrons are only paired when there are no more empty orbitals available within a sub-shell in which case the spins are
the opposite spins to minimise repulsion

When there are four electrons in a p subshell, one p orbital contains 2 electrons with opposite spin and two orbitals contain
one electron only

Notes Page 9
Inter-electrons repulsion

• Even though there is repulsion between negatively charged electrons (inter-electrons repulsion), they occupy the same region of
space in orbitals
• This is because the energy required to jump to successive empty orbital is greater than the inter-electron repulsion
• For this reason, they pair up and occupy the lower energy levels first

Electron Box Notation (orbital configuration)

• The electron configuration can also be represented using the electrons in boxes notation
• Each box represents an atomic orbital
• The boxes are arranged in order of increasing energy from lowest to highest
• The electrons are represented by opposite arrows to show the spin of the electrons (upward = positive spin)
○ Eg. the box notation for titanium is shown below
○ Note that since the 3d sub-shell cannot be either full or half full, the second 4s electron is not promoted to the 3d level and
stays in the 4s orbital

The electrons in titanium occupy the lowest energy levels first before filling those with higher energy

Hund's rule of maximum multiplicity

While filling the electrons in the orbital of a sub -shell having the same energy, the electrons will tend to fill in singly in all of the orbitals first.

Puali's exclusion principle

An orbital can only have electrons with the opposite spin.

Free radicals
• A free radical is a species with one or more unpaired electron
• The unpaired electron in the free radical is shown as a dot
○ Eg. a chlorine free radical has the electron configuration 1s22s22p63s23p5
○ Two of the three p orbitals have paired electrons whereas one of them has an unpaired electron
Arrangement of electrons in a chlorine radical

Ionisation Energy/ionisation potential/ionisation enthalpy

Ionisation is the process by which an electron is removed from an atom or a molecule

The ionization energy (IE) of an element is the amount of energy required to remove one mole of
electrons from one mole of gaseous atoms of an element to form one mole of gaseous ions

Amount of energy required to remove the most loosely-bound valence electron from the isolated gaseous
atom in its lowest energy state or ground state, in order to convert it into gaseous cation.

• Energy is required to remove an outer shell electron as this involves breaking the attractive forces
(electrostatic force) between the electron and the positively charged nucleus

Notes Page 10
• Ionisation energies are measured under standard conditions which are 298 K and 101 kPa
• The units of IE are kilojoules per mole (kJ mol-1)
• The values for ionisation energies are always positive as this is an endothermic process
○ This is because energy is required to break the force of attraction between the electron and the
central positive nucleus
Successive ionization energies
First ionization energy (IE1) Second/successive ionization energy (IE2)
the energy required to remove one mole of electrons energy required to remove one mole of electrons from
from one mole of atoms of an element to form one one mole of gaseous ions of an element to form one mole
mole of 1+ ions of gaseous 2+ ions
Monovalent cation is formed Divalent cation is formed

Because of the increase in effective nuclear charge

Trends in Ionisation Energy

• Ionisation energies show periodicity - a trend across a period of the Periodic Table

Four factors that affect the first ionisation energy

Size of the nuclear charge (+) Distance of outer electrons from Shielding effect of inner Spin-pair repulsion
the nucleus (atomic/ionic radius) electrons
- More atomic number, - Electrons in shells further away from the - More shells an atom has Electrons in the same atomic
- More nuclear charge, nucleus - Greater the shielding effect orbital in a subshell repel each
- Greater attractive forces between - Less attracted to the nucleus (weaker - Electrons in full inner shells repel other more than electrons in
nucleus and electrons nuclear attraction) electrons from outer shells different atomic orbitals which
- More energy required to overcome - Lower ionisation energy - Prevent them from feeling the full makes it easier to remove an
these attractive forces when (larger atoms/ions also result in greater nuclear charge electron (which is why the first
removing an electron shielding due to the presence of more - Less ionization energy ionisation energy is always the
inner electrons) lowest)

Tren Ionisation energy across a period Ionisation energy down a group There is a rapid decrease in ionization energy between
• The ionisation energy over a • The ionisation energy down a the last element in one period, and the first element in the next
d

Notes Page 11
 • The ionisation energy over a • The ionisation energy down a the last element in one period, and the first element in the next
d period
period increases group decreases
• Across a period the nuclear charge increases • The number of protons in the atom is increased, ○ There is increased distance between the nucleus and the
• This causes the atomic radius of the atoms so the nuclear charge increases outer electrons as you have added a new shell
to decrease, as the outer shell is pulled closer to • But, the atomic radius of the atoms increases as ○ There is increased shielding by inner electrons because
the nucleus, so the distance between the nucleus you add more shells of electrons, making the of the added shell
and the outer electrons decreases atoms bigger ○ These two factors outweigh the increased nuclear charge
• The shielding by inner shell electrons remain • So, the distance between the nucleus and outer
reasonably constant as electrons are being electron increases as you descend the group
added to the same shell • The shielding by inner shell
• It becomes harder to remove an electron as electrons increases as there are more shells of
you move across a period; more energy is electrons
needed • These factors outweigh the increased nuclear
• So, the ionisation energy increases charge, meaning it becomes easier to remove
the outer electron as you descend a group
• So, the ionisation energy decreases

Successive ionization energy data is helpful to predict the position of the elements in the periodic table.
The higher the energy of the electrons, the less ionization needed to remove.
Elements in fourth period doesn't follow the trend.

Table summarising ionisation energy trends across a period & down a group
Across a period: Down a group:
Ionization energy increases Ionization energy decreases
Increase in nuclear charge Increase in nuclear charge
The same number of shells Increased number of shells
Distance from the outer electron to the Distance from the outer electron to the
nucleus decreases nucleus increases
Shielding remains relatively constant Shielding increases
Decreased atomic / ionic radius Increased atomic / ionic radius
The attraction between the outer electron The attraction between the outer electron
and the nucleus gets stronger so the outer and the nucleus gets weaker so the outer
electron is harder to remove electron is easier to remove

Successive Ionisation Energies of an Element (second

ionization energy

Increases
- When the outer electron from an atom is removed, positive ion is formed (more difficult to move an
electron than a neutral atom)
○ Attractive forces increases in ion
1. Decreasing shielding
2. Increase in proton to electron ratio
• The increase in ionisation energy, however, is not constant and is dependent on the atom's
electronic configuration

Table Showing the Successive Ionisation Energies of Calcium Table

Electronic 1s2 2s2 2p6 3s2 3 1s2 2s2 2p6 3s2 1s2 2s2 2p6 3s 1s2 2s2 2p6 3s
Configuration p6 4s1 3p6 2 3p5 2 3p4
IE First Second Third Fourth
IE (kJ mol-1) 590 1150 4940 6480

Successive ionisation energies of an element

The ionisation energy increases as you remove more electrons from an element

• The first electron removed has a low IE 1 as it is easily removed from the atom due to
the spin-pair repulsion of the electrons in the 4s orbital
• The second electron is more difficult to remove than the first electron as there is
no spin-pair repulsion
• The third electron is much more difficult to remove than the second one corresponding
to the fact that the third electron is in a principal quantum shell which is closer to the
nucleus (3p)
• Removal of the fourth electron is more difficult as the orbital is no longer full, and there
is less spin-pair repulsion

Notes Page 12
Notes Page 13