COMPREHENSIVE NOTES

ATOMIC STRUCTURE &

ELECTRONIC STRUCTURE

OF THE ATOM
WORKED SOLUTIONS

@lcchemistry_tutor
 ATOMIC STRUCTURE & ELECTRONIC

STRUCTURE OF THE ATOM

Definition List
A triad is a group of three elements with similar chemical

Dobereiner’s

properties in which the atomic weight of the middle element is

triads approximately equal to the average of the other two.

Newlands
Newlands octaves: are arrangements of elements in which the first

and eighth element, counting from a particular element, have

octaves similar properties.

Mendeleev’s
When elements are arranged in order to increasing atomic

periodic law weight, the properties of the elements recur periodically.

Isotopes are atoms of the same element (i.e. they have the same

atomic number) which have different mass numbers due to the

Isotopes different numbers of neutrons in the nucleus.

The principle of mass spectrometry is that charged particles

The principle of
moving in a magnetic field are deflected to different extents

mass spec according to their masses and are thus separated according to

these masses.

Relative Atomic Mass is defined as: The average of the mass

Relative Atomic
numbers of the isotopes of the element, as they occur naturally,

taking their abundances into account and Eexpressed on a scale

Mass
in which the atoms of the carbon-12 isotope have a mass of
exactly 12 units.
 Definition List Continued

Energy Level An energy level is the fixed energy value of an electron in an atom.

Heisenberg's
It is impossible to measure the position and velocity of an electron

uncertainty
at the same time.

principle

Orbital A region in space where it is most likely to find an electron.

Paulie’s exclusion
No more than two electrons can occupy an orbital and when they

do they must have opposite spin.

principle

Electrons occupy the lowest energy level available when the

Aufbau principle electron is in the ground state.

When more than one orbital of equal energy exists, electrons

Hund's Rule tend to fill them singly before filling them in pairs.
 Definition List Continued

Atomic radius is half the distance between the centers of

Atomic radius neighbouring atoms which are joined together by a single covalent

bond

First ionisation
First ionisation energy is the energy required to remove the most

loosely bound electron from each atom in a mole of gaseous

energy atoms in the ground state.

Second ionisation energy is the energy required to remove the

Second ionisation
second electron from 1 mole of positive ions formed after the

energy first electron had been removed.

Electron negativity is the measure of the relative attraction atoms

Electronegativity in a molecule have for the shared pair of electrons in a single

covalent bond.

 Learning Objectives

Working knowledge of the periodic table. Differences

between the old and modern periodic table.

Concept that matter can be divided into elements,

atoms, ions, molecules

Ionic bonding as electron transfer

The Mass Spectrometer

Names of scientists and their corresponding

discoveries throughout history

Main points of Bohr's theory, evidence in support of

the theory and its limitations

How to carry out a flame test and corresponding

flame colour produces with 6 different salts

Understand the difference between and energy level,

a sublevel and an orbital

How to write electronic configurations

Trends in the periodic table

Scientists and their discoveries

Throughout this chapter, scientists are mentioned along the way with a brief explanation

of the experiments they carried out that led to the discovery of subatomic particles.
You do not need to know the type of experimentation carried out in detail apart from the

work of William Crookes and Rutherford. Other than that, the summary table below is

sufficient information to answer short questions.

History of the Atom

John Dalton

English chemist who summarised matter.

Daltons atomic theory: All matter is made up of tiny particles called atoms. All atoms are

indivisible i.e. Atoms cannot be broken down into simpler particles.

Discovery of the electron

William Crookes discovered cathode rays by placing an electric current through a glass

tube under low pressure. Low pressure allows for a vacuum so air particles can’t

Interfere with the cathode rays.

Cathode rays are negatively charged beams of electrons.
Important to note that it was cathode rays discovered by Crookes not electrons.
He did two experiments to discover the properties of cathode rays.

Experiment 1: The Maltese cross

Deduced that cathode rays travel in straight lines.

The rays themselves are invisible but do cause a shadow to be formed.
Cathode rays cause glass to fluoresce when they strike it.
Travel from the negative terminal of the battery towards the positive terminal.
Experiment 2: The paddle wheel

Same set up except a paddle wheel replaces the Maltese cross.

Cathode rays have enough energy to cause the paddle wheel to move.
Paddle wheel moves from negative terminal to positive terminal.

J.J Thompson

English scientist Thompson set up an experiment to deduce if the cathode rays have a

charge.
Cathode rays shone on the fluorescent screen undeflected provided if there was no

charge on the plates.

No charge meant the cathode ray travelled in a straight line.
As soon as the metal plates became charged, the cathode rays were deflected towards

the positive side.

Thompson deduced that the particles must be negative as they are deflected from the

negative plate. Like charges repels like charges.

Thompson is credited with the discovery of the electron.
Thompson eventually found the charge to mass ratio of the electron.
He did not figure out the charge of the electron itself nor its mass.

George Stoney

Galway man who named the negative particles or cathode rays as ‘electrons’ he however

is not credited with the discovery of electrons.

Milikan: Oil drop experiment i.e. measuring the charge on the electron

Robert Millikan set up an experiment to measure the charge of an electron.

He ionised the air in a small chamber by means of x-rays so the air molecules lost

electrons.
He sprayed tiny oil droplets in between two charged plates.
As the oil droplets fell they picked up electrons, thus becoming negatively charged.
Millikan adjusted the charges on the plates until he could get the oil droplet to be

suspended mid air.

This allowed him to discover the actual charge of the electron (1.6 x 10-19 Coulomb)

Thompson's Plum Pudding

Thompson stated an atom is like a positive sphere

with negative electrons embedded in it.
He was wrong but his depiction of an atom was
accepted for a long time before Rutherford came
along.

Discovery of the Nucleus

Ernest Rutherford discovered the nucleus and subsequently protons.

Rutherford bombarded a thin gold foil with alpha particles (positively charged particles).

Rutherford made 3 clear observations:

Most alpha particles went through with no deflection: the atom is composed of

mostly empty space.

Some alpha particles were deflected at large angles: the alpha particles are repelled

when they pass a small and positive nucleus.

A tiny amount of alpha particles were reflected straight back: The nucleus is very

dense.
Discovery of the proton

Rutherford kept experimenting with different metals and after multiple tests with the

same results concluded that the core of the nucleus contained positive particles

called protons.
Rutherford later concluded that electrons were outside the nucleus in some electron

cloud but it wasn’t until 10 years later that electrons were finally becoming

understood.

Discovery of the Neutron

James Chadwick discovered the neutron.

He bombarded beryllium with alpha particles however kept a paraffin wax block

behind the apparatus.

He found that another particle (neutral) was hitting the paraffin block.
Essentially the alpha particles break up the nuclei in beryllium and cause neutrons to

be expelled from the nucleus.

Because neutrons are neutral (no charge) they were the most difficult to detect.
Atomic Structure

The first accurate definition of an element was given by Robert Boyle:

An element is a substance that cannot be split into simpler substances by chemical

means.

Looking for a pattern in the periodic table

Dobereiner’s triads: A triad is a group of three elements with similar chemical

properties in which the atomic weight of the middle element is approximately equal to

the average of the other two.

Newlands octaves: are arrangements of elements in which the first and eighth element,

counting from a particular element, have similar properties.

Mendeleev’s periodic law: When elements are arranged in order to increasing atomic

weight, the properties of the elements recur periodically.

Moseley and the modern periodic table: In 1913, using X-rays, Mosley was able to

determine the number of protons in an atom of an element and this number is called

the atomic number. If elements were now placed in order of increasing atomic number

rather than atomic weight, elements fell naturally into the correct groups.

Differences between the modern periodic table and Mendeleev's table

Mendeleev's table:
Elements are ordered in terms of atomic weight,
Fewer elements present.
Gaps left for undiscovered elements.
Modern table
Elements are ordered in terms of atomic number.
More elements.
No gaps.

Isotopes are atoms of the same element (i.e. they have the same atomic number) which

have different mass numbers due to the different numbers of neutrons in the nucleus.

E.g. Carbon 12 and Carbon 13.

Relative Atomic Mass is defined as:

The average of the mass numbers of the isotopes of the element
As they occur naturally
Taking their abundances into account and
Expressed on a scale in which the atoms of the carbon-12 isotope have a mass of

exactly 12 units.
The Mass Spectrometer

Five stages of the spectrometer

Vaporisation. The sample is injected as a gas, or as a liquid that is heated to

vaporise it.
Ionisation. An electron gun forms positive ions by bombarding the atoms with high-

energy electrons which knock electrons off.

Acceleration. The positive ions produces pass between a series of negatively

charged plates. These plates accelerate these positive ions to high speeds.
Separation. An electromagnet deflects ions towards the detector. The lighter ions

are deflected the most.

Detection. The detector responds to the ions that hit it and produces a signal that

corresponds to the number of ions. A computer converts both measurements into a

spectrum on a paper recorder. The series of peaks is called a mass spectrum.

A mass spectrometer is used to:

Identify the presence of isotopes.
Measure the relative abundances of isotopes.
Measure relative atomic masses and relative molecular masses.
Identify unknown compounds.

Note: For the leaving certificate exam, you only need to know the 5 stages that occur

within the mass spectrometer and be able to identify where each stage occurs on a
diagram of a mass spectrometer.

The principle of mass spectrometry is that charged particles moving in a magnetic field

are deflected to different extents according to their masses and are thus separated

according to these masses.

Niels Bohr

In 1913, the Danish scientist Niels Bohr put forward his theory of energy levels in an

Atom. He based his theory on the analysis of emission spectra he obtained when he

excited hydrogen atoms in a discharge tube.

Main points of Bohr's theory

Electrons can only occupy certain areas within the atom, called energy levels.
An energy level is the fixed energy value of an electron in an Atom.
The ground state of an electron is when it occupies the lowest energy level available

to it.
When an electron absorbs energy, it jumps from a lower energy level to a higher

energy level. The electron is now said to be in an excited state. However, the

electrons are less stable in higher energy levels and tend to drop back down again to

lower levels.
When an electron drops from a higher to a lower level at definite amount of energy is

released in the form of a light of a particular frequency.

The definite amount of energy released when an electron drops from a higher to a

lower level is equal to the difference in energy between the two energy levels this

energy difference is given by the equation: E2 – E1 = hf

where E2 equals energy value of higher level
E1 equals energy value of lower level
H equals planck's constant
F equals frequency of light emitted
The energy levels are given a number called the principal quantum number the

lowest energy level is numbered N = 1.

Spectroscopic evidence to support Bohr’s theory

When negation elements such as hydrogen is electrically excited in a discharge tube the

electrons of the hydrogen atoms absorb the energy and then give off energy in the form

of light. When this life was examined, a line spectrum was obtained.

Mandatory experiment: flame test evidence to support Bohr's theory

Procedure

Clean a platinum wire thoroughly, in a fume cupboard, using concentrated hydrochloric

acid.
Place the wire in a bunsen flame, making sure it imparts no colour to the flame.
Dip the wire in a clean sample of hydrochloric acid and then into a sample of the salt to

be tested.
Hold the wire with the salt in the bunsen flame and note the colour given off.
Repeat the above steps for different salts and note the colour in each case.

Why does the flame test represent evidence for Bohr's theory?

When metal salts of a particular element is heated the electrons emit light of a certain
colour as electrons drop back down from higher to lower levels.

Why does each element produce its own unique atomic spectrum?

Each element produces its own particular colour as each element has a certain number

of electrons which are arranged in certain energy levels. Therefore, different electron

transitions are available to that element and thus a different line spectrum is produced

by each element.

Everyday uses of emission spectrum

Fireworks: salts of strontium and barium are used in firework displays.

Lasers make use of light released by electronic transitions.

Atomic absorption Spectra

Atomic absorption spectrum is the spectrum that is obtained when light is passed

through a gaseous sample of an element.

An atomic absorption spectrometer is used to analyse samples of water or blood for

heavy metals such as lead or Mercury.

The main principle of atomic absorption spectrometry is that atoms of an element

absorb light of a certain frequency which is particular to that element. The amount of

light absorbed is directly proportional to the concentration of that element. During the

process, light which is characteristic of the element is passed through an atomised

sample of the element in the spectrometer. The amount of light absorbed by the sample

is measured by the spectrometer and this information can be used to estimate the

concentration of that element present.

Energy levels and sublevels

In a closer and more exact study of the emission line Spectra of elements it was noted

that what appeared to be a single line on a line spectrum was really two or more lines

which were very close together.

To explain this, scientists proposed that each main level excluding the 1st was made up

of a number of sublevels.
The sublevels were assigned the letters s, p, d and f in order of their energy value. The s

sublevel was given the lowest energy, and the f sublevel was given the highest energy.
The number of sublevels is the same as the number of the main level. Therefore, the
main level one has one sublevel called the 1s, the second main level, 2, has two

sublevels, the 2s and 2p sub levels and so on.

Modern improvements on Bohr’s theory

Bohr's model of the Atom where he envisaged electrons as particles revolving around

the nucleus was developed and modified by scientists in the 1920s and 1930s.
In 1923 the French scientists Louis de Broglie proposed that electrons had wave

properties, and this was shown experimentally to be correct. Electrons were now said to

have both a particle and wave nature.

If an electron has a wave nature, then it could not have a definite path about the nucleus

as Bohr had proposed.

Furthermore, the German physicist Heisenberg put forward his uncertainty principle

about the difficulty of locating the position of an electron in an atom.

Heisenberg's uncertainty principle states that it is impossible to measure the position

and velocity of an electron at the same time.

Then the Austrian scientist Erwin Schrödinger developed mathematical equations to

describe the probability of finding an electron in an Atom. As a result of Schrödinger’s

work, orbitals were used to describe the movement of electrons in an Atom.

An atomic orbital is a region of space where it is most likely to find an electron.

Properties of atomic orbitals

It is required that you know the shapes of the s and p orbitals.

Each orbital can hold 2 electrons.

This follows Paulie’s exclusion principle where he stated that no more than two

electrons can occupy an orbital and when they do they must have opposite spin.

Aufbau principle: Electrons occupy the lowest energy level available when the electron

is in the ground state.

The s orbitals are spherical there is only one s orbital for each sublevel.
The p orbitals have a dumbbell shape. There are three p orbitals for each sub level. They

are called the px, py and the pz orbitals.

These p orbitals are at right angles to each other as shown in the diagram. It is important

to note that any p sublevel can accommodate 6 electrons.

There are five d orbitals. It is not required that you know the names or shapes of these

orbitals. It is important to note that the d sublevel can accommodate 10 electrons.

Electronic configurations of atoms

The arrangement of electrons in the various sub levels is called the electronic

configuration. The electronic configuration of the first 36 elements is required for the

leaving certificate.

Example 1: s,p type configurations

Write out the electronic configurations of carbon, oxygen and nitrogen explain why

nitrogen has extra stability.

To explain nitrogen’s extra stability the arrangement of electrons in the individual

orbitals of the two p sublevel must be examined.

Nitrogen has extra stability as the two-p sub level is half full and a half full sublevel is

the next most stable to a full sublevel.

Note that the individual 2p orbitals are filled singly before filling them in pairs the above

configurations are an example of Hund’s rule.

Carbon: 1s2, 2s2, 2px1, 2py1

Nitrogen: 1s2, 2s2, 2px1, 2py1, 2pz1
Oxygen: 1s2, 2s2, 2px2, 2py1, 2pz1
Example 2: s,p,d electronic configurations

Write out the electronic configurations of scandium, chromium and copper and explain

why copper and chromium have unusual configurations.

Scandium has 21 electrons, and its electronic configuration is:
Scandium (Sc): 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d1
Chromium has 24 electrons and its electronic configuration is:
Chromium (Cr): 1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d5
Note the unusual configuration of chromium where one of the four S electrons

moves into the 3D sublevel. Two half-filled sublevels give extra stability.

Electronic configuration of ions

What is the electronic configuration of the magnesium ion Mg2+? What neutral atom has

the same configuration?

The magnesium atom has 12 electrons and therefore the magnesium ion has 10

electrons as it has lost 2 electrons. Therefore, the electronic configuration of the

magnesium ion is:

Mg2+: 1s2, 2s2, 2p6
This ion has the same configuration as neon

Trends in the periodic table

In your leaving cert exam, you may be asked to state a trend in atomic radius, ionisation

energy or electronegativity either across or down the periodic table. You must also be

able to justify your answer.

Atomic radius is half the distance between the centers of neighbouring atoms which are

joined together by a single covalent bond. For example, the atomic radius of hydrogen is

half the distance between the nuclei of the two hydrogen nuclei which are covalently

bonded.

First ionisation energy is the energy required to remove the most loosely bound

electron from each atom in a mole of gaseous atoms in the ground state.
Second ionisation energy is the energy required to remove the second electron from 1

mole of positive ions formed after the first electron had been removed.

Electronegativity is the measure of the relative attraction atoms in a molecule have for

the shared pair of electrons in a single covalent bond.

Important Trend Terms

Effective nuclear charge: the net positive charge from the nucleus that an electron can

“feel” attractions from. The core electrons are said to shield the valence electrons from

the full attractive forces of the protons in the nucleus.

Shielding: core (non-valence) electrons shield the valence electrons from the full

attractive forces of the protons in the nucleus.

Electron-electron repulsions: due to their like charges, electron pairs orient themselves

as far away as possible from each other, causing the electron cloud to expand (justifies

trends across a period).