PHYSICAL CHEMISTRY

ATOMIC STRUCTURE

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Overview
 Atom
 Subatomic particles
 Proton number and nucleon number
 Isotopes
 Atomic structure
 Electronic configuration of atoms and ions
 The Octet Rule
 Ionization energy
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 Atom
 The Atom – Basic unit of an element that can take part in a chemical
reaction.

 Modern Atomic Theory

1. All matter is made up of very tiny particles called atoms.

2. Atoms of the same element are chemically alike.
3. Individual atoms of an element may not all have the same mass.
However, the atoms of an element have a definite average mass
that is characteristic of the element.
4. Atoms of different elements have different average masses.
5. Atoms are not subdivided, created, or destroyed in chemical
reaction.

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Subatomic particles

1
0

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 Subatomic particles
Behaviour of beams of protons, neutrons and electrons in electric field and magnetic field

 Protons and electrons are

deflected by both electric and
magnetic fields, but in opposite
directions.
 Neutrons are not deflected at all.
 The size of the deflection
depends on the relative masses
of the particles.

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Proton Number (Z) and
Nucleon Number (A)

Nucleon number 23
Proton number 11
Na

 Nucleon number = n + p
 Proton number = p

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 Proton Number (Z) and
Nucleon Number (A)
Proton Nucleon
Protons Neutrons Electrons Charge Symbol
Number Number

A 19 21 19

B 20 0 40

C + 11 23

D 6 6 0

E 92 0 235

F 6 13

G 16 2- 16

H 27Al3+
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Isotopes
 Atoms of the same element which have the same
number of protons, but vary in the number of
neutrons.
 Have different masses.
 Do not differ significantly in their chemical behavior.

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 Isotopes
Isotopes of an element have:

Same Different

 Proton number  Number of neutrons in an

 Number of electron in atom.
neutral species.  Nucleon number.

 Electronic configuration  Relative isotopic mass.

 Chemical properties  Physical properties (density)

 Rate of diffusion

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Uses of radioisotopes
 As tracers in biological processes. Example: the
uptake of phosphorous by plants can be traced
using the radioactive 32P isotope.
 14C is used in “carbon dating”, a technique used

to determine age of archaeological artifacts.

 γ-radiation from 60Co is used in radiation therapy
to destroy malignant tissues in cancer patients
 The energy released during nuclear fission is
used to generate electricity in nuclear reactors.

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Atomic Structure

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 Atomic Structure
Bohr’s Model
• Electron as particle
• Electron orbit in FIXED radius from nucleus
Electron – particle
Quantum Model
• Electron as standing wave around nucleus
• Electron NOT in fixed position
• ORBITAL – probability/chance finding electron
• Electrons arrange in specific energy level and
sublevels.
• Each electron is a wave that can be described by a
series of “quantum numbers”.
Electron – Wave like nature

Orbit

Orbital

Orbit – circular path of an electron around

the nucleus.
Nucleus
Orbital – region (or volume) in space
around the nucleus where the probability
finding a particular electron is high. Electron cloud 12
Quantum mechanics
model
 Heisenberg’s uncertainty principle – It is
impossible to know precisely both the velocity and
location of an electron at the same time.
 We cannot know how the electron travels around the
nucleus we can know where it spends the majority of
its time.
 The “probability” of finding an electron around a
nucleus can be calculated.
 Relative probability is indicated by a series of dots,
indicating the “electron cloud”.

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 Quantum mechanics
model
 Electrons move rapidly and randomly around the nucleus
 Electrons have discrete energies, not because they are in shells but
because they can only have certain wavelengths.
 Electron NOT in fixed position
 Electrons are found a long way from the nucleus in a series of level called
energy level (arranged in shells).
 Each energy level (shell) can only hold a certain amount of electrons
 Known as Principal quantum numbers- a set of quantum numbers of an
atomic orbital.
 Shell – a group of orbitals that are about the same distance out from
nucleus.
 Shell number : 1, 2, 3, etc
 Each shell consists of subshells (a group of orbitals with same energy level,
but different orientation in space): s, p, d, f
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 Quantum mechanics
model
Principal quantum number (n)
 Main energy level occupied by electrons
 Positive integer: n=1, 2,3….
 Distance from nucleus, (higher n – higher energy)

Angular momentum quantum number (l)

 Indicate the shape of the orbital.
 l depends on n
 l = 0, 1, 2…….n-1

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Quantum mechanics
model


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 Four Quantum Numbers

• Electrons arrange in specific energy level and sublevels No TWO electron have same
• Orbitals of electrons in atom differ in size, shape and orientation. 4 quantum number
• Allow states call orbitals, given by four quantum number 'n', 'l', 'ml' and ’ms’ - (n, l, ml, ms)

1 Principal Quantum Number (n): n = 1, 2, 3,.. ∞ 3 Magnetic Quantum Number (ml): ml = -l, 0, +l.
• Energy of electron and size of orbital/shell • Orientation orbital in space/direction
• Distance from nucleus, (higher n – higher energy) • mℓ range from −ℓ to ℓ,
• Larger n - farther e from nucleus – larger size orbital • ℓ = 0 -> mℓ = 0 –> s sublevel -> 1 orbital
• n=1, 1stprincipal shell ( innermost/ground shell state) • ℓ = 1 -> mℓ = -1, 0, +1 -> p sublevel -> 3 diff p orbitals
• ℓ = 2 -> mℓ = -2, -1, 0, +1, +2 -> d sublevel -> 5 diff d orbitals
• (2l+ 1 ) quantum number for each ℓ value

2 Angular Momentum Quantum Number (l): l = 0 to n-1. 4 Spin Quantum Number (ms): ms = +1/2 or -1/2
• Orbital Shape • Each orbital – 2 electrons, spin up/down
• Divides shells into subshells/sublevels. • Pair electron spin opposite direction
• Letters (s, d, p, f) • One spin up, ms = +1/2
• One spin down, ms = -1/2
s orbital
• No net spin/cancel out each other– diamagnetic electron
p orbital

writing electron spin

electron spin up/down

d orbital

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Shapes of Orbital

s orbital

d orbital

p orbital
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Electronic Configuration of
atoms and ions

Type of subshell Number of

orbitals
s 1
p 3
d 5
f 7

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 Electronic Configuration of
atoms and ions

Principal Orbitals Maximum

quantum number of
number electrons (2n2)
(Shell number)
1 1s 2
2 2s, 2p 8
3 3s, 3p, 3d 18
4 4s, 4p, 4d, 4f 32
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Electronic Configuration of
atoms and ions
 Orbital energy level

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Electronic Configuration of
atoms and ions
Electrons are arranged in orbitals according to these rules:
 Maximum 2 electrons in each orbitals (Pauli Exclusion Principle)
 Fill the empty orbital with the lowest energy (Auf Bau
Principle) .
 Must occupy all orbitals of equal energy before paring up
(Hund’s Rule).
 Electrons can spin in 2 different directions, ↑ and ↓:

- 2 e- in same orbital have opposite direction.

↑↓

- single electrons in the same subshell have same spin

↑ ↑
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Electronic Configuration of
atoms and ions
 Electronic configuration of transition elements (Z=21
to Z= 30), the energy level of 4s orbital is lower than
that of the 3d orbitals.
Example: Ca

Sc
 However, once electron(s) is/are filled into 3d orbital,
the order is reverse. The 3d orbitals now have lower
energy than 4s orbital.
Example: Sc3+
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Electronic Configuration of
atoms and ions
 In the formation of cations, electrons are removed in
reverse order from electron filling
- the last electron is removed first.
Example: O+

Fe2+
 In the formation of anions, electrons are added in the
same manner as the filling of electrons in the neutral
atoms.
O2-
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Electronic Configuration of
atoms and ions
 Isoelectronic – Atoms or ions that have
the same number of electrons.
Example: H2O, Na+, Al3+, F- (10e-)

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Electronic Configuration of
atoms and ions
Exceptions of electronic configuration:

24Cr : 3d54s1, not 3d44s2

- half-filled 3d subshell, more stable.

 29Cu : 3d104s1, not 3d94s2

- full-filled 3d subshell, more stable.

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The Octet Rule
 Noble gas electron arrangement: stable
 Atoms form ions by losing or gaining
electrons.
 Atoms form molecules by sharing
electrons.
 Octet rule does not apply well to
transition elements.

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Ionisation Energy
 1st ionisation energy: Amount of energy required to
remove one mole of electron from one mole of
gaseous atoms of the element to produce one mole
of gaseous cations with +1 charge.

 When more than one electron is removed: 2nd

ionization energy, etc

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Ionisation Energy
 Ionisation energies normally have positive value
(energy is absorbed in removing electron).

 The succesive ionisation energies of an element

increase with the removal of electron
- remaining electrons are attracted more strongly by
constant positive charge on the nucleus.

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 Ionisation Energy
 Ionisation energy of depend on
(1) Size of atom / ion
- Atomic size/ion increases, the attraction of
positive nucleus for electron decreases.
- Less energy is required to remove an electron

(2) The nuclear charge

- The number of proton increases, nuclear
charge increases, its attraction for the outermost
electron increases.
- more energy is required to remove an electron. 30
Ionisation Energy
(3) Screening (shielding) effect of inner
electrons
- The outermost electrons is screened (shielded)
from the attraction of the nucleus by the repelling
effect of the inner electrons.
- Shielding increases, the attraction of the
positive nucleus for the negative electron decreases.
- Less energy is required to remove an electron.

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Ionisation Energy
 Ionization energy decreases down the group.
- Atomic radius ↑, due to increasing number
of shells of electrons.
- outer electrons are further from nucleus,
better shielded by inner shells electrons.
- less attracted by positive nucleus.

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Ionisation Energy
 Ionisation energy increases across a
period, with increasing proton number
and decreasing atomic radius.
- all electrons go into the same shell,
shielding effect is about the same.
- The outer electrons are more strongly
attracted by the positive nucleus.

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Ionisation Energy

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 Ionisation Energy
 Period 3
 1st ionization energy of Mg>Al
Mg 3s2
Al 3s2 3p1
- The 1st electron is removed from 3p orbital of Al as compared to
3s orbital for Mg.
- 3p orbital is at a higher energy level than 3s orbital (further away
from the nucleus)
- 3p electron is also better shielded by 2 inner 3s electron.
- single electron from 3p orbital in Al is easily removed

 Same explanation for Be/B from period 2.

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Ionisation Energy
 1st ionization energy of P>S
P 3s2 3p3
S 3s2 3p4
- The 1st electron removed from phosphorus is from a stable
half-filled 3p orbital.
- For S, the electron removed from sulphur is from the orbital
which contains a pair of electrons. There is repulsion between
the pair of electrons (spin-pair repulsion)
- Electron is easily removed.

 Same explanation for N/O from period 2.

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Ionisation Energy
 1st ionization energy of Ne>Na
Ne 2s2 2p6
Na 2s2 2p6 3s1

- The outer electron of Na is in the 3rd shell (3s

orbital) and is further away from the nucleus than
the outer electron of Ne.
- The outermost 3s electron in Na experiences more
effective shielding by the inner shell electrons.

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Ionisation Energy

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 Ionisation Energy
 The following information can be obtained from
successive ionisation energy data:
(a) Total number of electrons in an atom
(b) Number of quantum shells occupied and number
of electrons in each.
(c) Number of subshells occupied and the number of
electrons in each.

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Ionisation Energy
 Successive ionisation energies of Al

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Ionisation Energy
Question
The first seven successive ionization energies for an element are
as follows (in kJ/mol)
790 1600 3200 4400 16100 19800 23800

(a) How many electrons are there in the outer shell of the element?
(b) Which group in the periodic table does the element belong?
Explain your answer.
(c) Write down the outer electronic configuration of the element.

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Ionisation Energy
Question
For the following successive ionisation energy, deduce which
group does the element belong and write down the outer
electronic configuration.

1. 578 1817 2745 11578 14831 18378

2. 786 1580 3230 4360 16000 20000 23600 29100

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