CHEMISTRY

Atomic Structure
Vicky Xie
The nuclear atom Electron configuration

CONTENTS
The nuclear
atom

01
01 Dalton’s atomic theory

Dalton called the indivisible building blocks that comprise matter “atoms”.
Dalton’s theory can be summarized as follows.
• Postulate 1: All matter (materials) consists of very small particles
called atoms.
• Postulate 2: An element consists of atoms of one type only.
• Postulate 3: Compounds consist of atoms of more than one element
and are formed by combining atoms in whole-number ratios.
• Postulate 4: In a chemical reaction atoms are not created or destroyed.
02 Discovery of electron

J.J. Thomson studied electric discharge using cathode-ray tubes.

02 Cathode-ray tube experiment
The ray was produced at the negative electrode and was repelled by the
negative pole of an applied electric field.

discover the electron

Deflection of Cathode Rays by an Applied Electrical Field

03 Plum-pudding model
04 Gold foil experiment

Rutherford’s experiment on α particle (high-energy, positively charged He2+

ions emitted from naturally occurring radioactive elements such as radium)
bombardment of a gold foil:
The α particles would decelerate Some particles were deflected by very
but minor deflection. large angles and some even bounced
straight back towards the source.
Discovery from gold foil experiment

• Atom has a dense center of

positive charge called nucleus.
• Electrons travel around the
nucleus at a large distance
relative to the nucleus.
 05 The nuclear atom

No charge
Positive charge (+)
Positive charge (+)

Negative charge (-)

 05 The nuclear atom

1 amu = 1.660539×10-24 g
• The size of the atom is determined by the movement of electrons.
• The mass of the atom is determined by nucleus.
06 The nuclear symbol

Mass number A
Atomic number Z X
atomic number = No. of protons = No. of electrons = nuclear charge

Mass number = No. of protons + No. of neutrons

(A) (Z) (N)
 07 Ions

Ions are charged particles that are formed

when an atom loses or gains (an) electron(s).

A positive ion (cation) is formed when an

atom loses (an) electron(s) so that the ion
has more protons(+) than electrons(−).

A negative ion (anion) is formed when an

atom gains (an) electron(s) so that the ion
has more electrons(−) than protons(+).
Example. Deduce the number of protons, neutrons, and electrons for the
atom with this atomic symbol:
37 −
17Cl

Solution:
No. of protons = 17
No. of neutrons = 37 - 17 = 20
No. of electrons = 17+1 = 18
Example. Which species contains 16 protons, 17 neutrons and 18 electrons?
A. 32S-
B. 34S-
C. 33S2-
D. 35S2-
 08 Isotopes

Isotopes are different forms of the same element that have the same
atomic number/proton number, Z, but different mass numbers, A, because
they have different numbers of neutrons in their nuclei.

Isotopes have the same chemical properties but different physical

properties (e.g. different melting points and boiling points).
07 Isotopes

protium
deuterium (D)
tritium (T)
Example. Deduce the number of protons, neutrons, and electrons for the
atom with this atomic symbol:
37
17𝐶𝑙

Solution:
No. of protons = 17
No. of neutrons = 37 - 17 = 20
No. of electrons = 17
 09 Radioactive isotopes

Radioactive isotope, also called radioisotope, are unstable and release

excess energy by spontaneously emitting radiation in the form of alpha, beta,
and gamma rays.

𝛼-particle production 𝛽-particle production 𝛾-particle production

238
238
92𝑈 → 42𝐻𝑒 + 234
90𝑇ℎ
131
53𝐼 → 0
−1𝑒 + 131
54𝑋𝑒 92𝑈 → 42𝐻𝑒 + 234
90 𝑇ℎ + 2 0
0𝛾

Radioisotopes are used in nuclear medicine for diagnostics, treatment, and

research, as tracers in biochemical and pharmaceutical research, and as
“chemical clocks” in geological and archaeological dating.
 09 Radioactive isotopes

Positron emission tomography (PET) scanners give three-dimensional images

of tracer concentration in the body, and can be used to detect cancers.
 10 Carbon dating

The half-life, t1/2 is the time it takes for an amount of radioactive isotope to
decrease to one-half of its initial value.

14
6𝐶 → 14
7𝑁 + −10𝑒

• The net result is that there is a gradual decrease in the ratio of carbon-
14 to carbon-12 in the organism’s body.
• The amount of carbon-14 in the body of a plant or animal that was
once living can be measured.
09 Relative atomic mass

The relative atomic mass (Ar) of an element is the average of the masses of
the isotopes in a naturally occurring sample of the element relative to the
mass of 1/12 of an atom of carbon-12.

Abundance: the mass percentage of an isotope in the natural environment.

1.10%
C-12
C-13

98.90%
 09 Relative atomic mass

Relative atomic mass: the weighted average of the relative masses of the
isotopes.

Isotope Relative atomic mass Abundance (%)

12C 12 98.90%
13C 13 1.10%

Relative atomic mass

= (12)(98.90%) + (13)(1.10%) = 12.01
of carbon
 10 Mass spectrometer

The degree of deflection

depends on the mass-to-
X(g) + e- → X+(g) + 2e- charge ratio (the m/z ratio).
 11 Mass spectra

The number of
peaks tell the
number of isotopes.
The abundance
are 75% and 25%.

The relative mass of

isotopes are 35 and 37.

Mass spectrum of Cl
11 Mass spectra

Relative Relative
Isotope
isotopic mass abundance (%)
35Cl 34.969 75.80%
37Cl 36.966 24.20%

• Average relative atomic mass of Cl:

• = 34.969 × 75.80% + 36.966 × 24.20% = 35.45
Example. Iridium has a relative atomic mass of 192.22 and consists of Ir-191
and Ir-193 isotopes. Calculate the percentage composition of a naturally
occurring sample of iridium.
 Electron
configuration

02
 01 Electromagnetic spectrum

decrease
Wavelength
 01 Properties of electromagnetic radiation

• Wavelength 𝝀: distance between

identical points on successive waves.
• Frequency 𝝂: the number of waves
that pass through a particular point
in 1 second. (unit: s-1 or Hz)
• Speed of light c (3×108 m/s) c = 𝜆𝜈

1
𝜈∝
𝜆
 01 Electromagnetic spectrum

Frequency increase
decrease
Wavelength
 02 Refraction of light
Refraction, in physics, the change in direction of a wave passing from one
medium to another caused by its change in speed.
 Emission spectrum
is a spectrum produced by emitting light of various wavelengths.

White light produces a continuous spectrum containing all the wavelengths

of visible light from red to violet.
 Emission spectrum
• Each line corresponds to a light with a specific wavelength.
 Emission spectrum
• Every element has a unique emission spectrum.
• Line spectrum can be used in chemical analysis as fingerprints are used
to identify people.
If a cloud of a cold gas is
placed between a hot metal
and a detector, an absorption
spectrum is observed.
03 Quantization of energy

Energy of a photon:
𝑐
E = h𝜈 = h
𝜆

h = Planck’s constant = 6.63×10-34 J·s

𝜈 = frequency of the radiation
c = speed of light = 3.00×10-8 m s-1

E is inversely proportional to 𝜆
 04 Bohr’s theory of the hydrogen atom

• Electron in a hydrogen atom moves

nucleus
around the nucleus in circular orbits.
• Each orbit has a particular energy, the orbit
energy of the electron orbiting the
n=1
positively charged center in a particular
electron n=2
orbit is fixed or quantized. n=3
n=4
 03 Quantization of energy

• The energy of the electron in orbits are quantized.

• The energy of the electron

1
E= -RH ∙ ( 2 )
𝑛

RH = Rydberg constant = 2.18× 10-18 J

n = principal quantum number, n = 1, 2, 3, 4, ...
The ball can rest on any
step but not between steps.
 05 Energy level

1
E= -RH ∙ ( 2 )
𝑛

• If the electron were at an infinite distance from the nucleus (n = ∞) ,

there is no interaction and the energy is zero:
1
E= -18
-2.178×10 J( )=0
∞2

• The negative sign means as n decreases, the energy of electron decreases.

 05 Energy level
• When electron jumps to a higher energy level, it will absorb energy.
• When electron falls to a lower energy level, it will release energy.
05 Energy level

Convergence:
The lines in the emission spectrum get closer together at higher energy.
 05 Energy level

Ground state Excited state

The lowest energy state of the When an electron absorb energy, the
electron is called ground state. electron will jump to a higher energy
level. This state is called excited state.
Example. Calculate the change in energy of an electron when an electron
in level n = 6 falls back to level n = 1.
Solution: excited state
1
∆E = Ef – Ei E = -RH ∙
𝑛2

1 1 1 1
∆E = Ef – Ei = -RH ∙ + RH ∙ = RH 2 −
𝑛𝑓 2 𝑛𝑖 2 𝑛𝑖 𝑛𝑓 2
= -2.117×10-18 J

• The negative sign indicate that the atom has

lost energy and is now in a more stable state.
ground state
• The energy is carried away from the atom by
the emission of light.
06 Series of lines in the emission spectrum
06 Series of lines in the emission spectrum
 07 How an emission spectrum is formed

1. Electron is excited when absorbs energy from the

discharge tube.
 07 How an emission spectrum is formed

2. The excited electron (n = 4) will fall

back to the ground state (n = 1) by
emitting a photon with energy h𝜈.
 07 How an emission spectrum is formed

• The value of h𝜈 is equal to the

difference in energies of the two orbits.

1 1 𝑐 photon
∆E = RH 2 − = h𝜈 = h
𝑛𝑖 𝑛𝑓 2 𝜆
 07 How an emission spectrum is formed

• There will be different ways for

the electron to fall back to the
ground state.
• Each ∆E corresponds to a different
𝜆, thus different colors of light.

❶ ❷ ❸ ❹
 08 Bohr model

• The model correctly fits the quantized energy levels of the hydrogen
atom and postulates only certain allowed circular orbits for the electron.
• As the electron becomes more tightly bound, its energy becomes more
negative relative to the zero-energy reference state (electron being at
infinite distance from the nucleus).
• As the electron is brought closer to the nucleus, energy is released from
the system.
 08 Bohr model

Insufficient for the Bohr model:

Bohr model is incorrect for atoms other than hydrogen.
Electrons do not move around the nucleus in circular orbits.

However, Bohr model is important because it fits the quantization of

energy and it paved the way for later theories.
 09 Quantum mechanical model of the atom

Heisenberg uncertainty principle:

There is a fundamental limitation to just how precisely we can know both
the position and momentum of a particle at a given time.

ℎ
∆𝑥 ∙ ∆(𝑚𝑣) ≥
4𝜋

Where ∆x is the uncertainty in a particle’s position, ∆(mv) is the uncertainty

in a particle’s momentum, and h is Planck’s constant.
 10 Schrodinger’s equation

The solution to Schrodinger’s equation generated a series of mathematical

functions called wavefunctions , ψ, describing the electron in the
hydrogen atom and associated possible energy states the electron can
occupy. The square of the wavefunction, ψ2, represents the probability of
finding an electron in a region of space at a given point a distance, r, from
the nucleus of the atom. ψ2 is termed the probability density.
11 Probability density

1s orbital showing the probability

of finding the electron at different
distances from the nucleus
 12 Atomic orbital

An atomic orbital is a region in space where there is a high probability of

finding an electron.

Any orbital can hold a maximum of two electrons. There are several types
of atomic orbital: s, p, d, and f, etc.

s orbital p orbital
 12 Atomic orbital

An s orbital is spherically symmetrical.

The s orbitals become larger as the value of n increases.

12 Atomic orbital
A p orbital is dumbbell shaped.
13 Sublevels

The energy levels are splits up into sublevels.

Each sublevel can hold a maximum of two electrons.
 13 Sublevels

n Sublevel Number of orbitals Maximum number of electrons

1 1s 1 2
2 2s 1 2
2p 3 6
3 3s 1 2
3p 3 6
3d 5 10
4 4s 1 2
4p 3 6
4d 5 10
4f 7 14
14 Orbital diagrams

s sublevel

p sublevel
“arrow-in-box” notation
d sublevel

f sublevel
 15 Quantum numbers

Principal quantum number, n

• Represents the energy level;

• As n increases, the mean position of an electron is further from the nucleus;
• As n increases, the energies of the orbitals increase.

Spin magnetic quantum number, ms

1 1
• ms = + or -
2 2
 16 Electron configuration
Aufbau principle states that electrons fill the lowest-energy orbital that is
available first.

The order is: 1s < 2s < 2p < 3s < 3p < 4s < 3d < …
 16 Electron configuration

For hydrogen atom, the electron configuration is 1s1:

16 Electron configuration

Orbital diagram:
The arrow represents an electron
spinning in a particular direction

According to Pauli exclusion principle,

the electrons should have opposite spin.
16 Electron configuration
16 Electron configuration

Hund’s rule of maximum multiplicity: electrons fill all the orbitals

singly before occupying them in pairs.
16 Electron configuration
 17 Condensed electron configuration

A more convenient way of representing electron configurations is as the

condensed electron configuration:
[nearest noble gas] + valence electrons

For example:

Na 1s22s22p63s1 [Ne]3s1 He 1s2 [He]

O 1s22s22p4 [He]2s22p4
16 Electron configuration

K (19) 1s22s22p63s23p64s1 [Ar]4s1

Sc (21) 1s22s22p63s23p63d14s2 [Ar]3d14s2

Fe (26) 1s22s22p63s23p63d64s2 [Ar]3d64s2

18 Chromium and copper - exceptions

Cr (24) 1s22s22p63s23p63d54s1 [Ar]3d54s1

3d orbitals are half-filled

Cu (29) 1s22s22p63s23p63d104s1 [Ar]3d104s1

3d orbitals are completely filled

Half-filled (3d5) and completely filled (3d10) are slightly more stable.
18 Orbital diagrams
Orbital diagrams may have steps showing the energy levels or may be
represented on one line.