STRUCTURE OF AN ATOM

• Atom is the smallest particle of an element that retains

the chemical nature of the element.

• The smallest particle of an element that has all the

properties of that element

• Extremely small particle of matter that retains its

identity during chemical reactions
 GENERAL CHEMISTRY 1
• CHEM 1101
• Course outline

Lecturer : “Dr” Charles Luhana

 ATOMIC THEORY OF MATTER
The British chemist John Dalton (1766–1844) provided the
basic theory:
that all matter-whether element, compound, or
mixture - is composed of small particles called atoms.

The Postulates of Dalton’s Atomic Theory

1. All matter is composed of indivisible atoms.
2. An element is a type of matter composed of only one
kind of atom.
-Each atom of a given kind having the same
properties.
-Thus, the atoms of a given element have
a characteristic mass.
 ATOMIC THEORY OF MATTER
cont..
3. A compound is a type of matter composed of atoms
of two or more elements chemically combined in fixed
proportions.

4. atoms are not created, destroyed, or broken into

smaller particles by any chemical reaction.

NB: It is known that atoms are not truly indivisible; they

are made up of particles.
- Nucleus
- One or more electrons.
 Light and Electrons

• We tell what electrons are “doing” by observing

light
• Light behaves as a wave when travelling through
space.
• Light behaves as a particle (photon) when
interacting with matter.
 Light as a Wave
• Light waves have properties of speed, wavelength
and frequency.

c = 
speed of light frequency
wavelength s -1

m s-1 m
 Textbook: See also
Examples 7.1 and 7.2
Problem 1 Exercise 7.1 and 7.2

• Calculate the frequency of one photon of blue

light (of wavelength exactly 461nm).

c=2.998 x 108 m s-1

h=6.626 x 10-34 J s
 Light as a particle
• Light consists of quanta or particles of
electromagnetic energy, called photons.
• The energy of each photon is proportional to its
frequency:
nu

E = hn

h = 6.626 × 10-34 J  s (Planck’s

constant)
 Textbook: See also
Examples 7.3
Problem 2 Exercise 7.3

• In Problem 1 we determined that the frequency ν

of light (of wavelength) 461nm is 6.50 x 1014 s-1
(using c=λν).

c=2.998 x 108 m s-1

h=6.626 x 10-34 J s
 Electrons

• Light absorbed and emitted by atoms, is

absorbed or emitted by the electrons in the atom.
• The electron will gain energy from a photon, or it
will lose energy by releasing a photon.
 Emission and Absorption Spectra

Colored flames from several metal compounds; the visible light

is emitted from the metal atoms.
The yellow emission from sodium atoms is used in sodium
streetlamps.
 Emission and Absorption Spectra

• Light from a heated gas, dispersed through a

prism shows only some wavelengths
Emission and Absorption Spectra
sample
The Bohr Theory of the atom

ni=4, nf=2
The Bohr Theory of the atom

photon released

ni=4, nf=2
The Bohr Theory of the atom

ni=3, nf=2
The Bohr Theory of the atom

photon released

ni=3, nf=2
The Bohr Theory of the atom

ni=2, nf=4
The Bohr Theory of the atom

ni=2, nf=4
 The Bohr Theory of the atom

• Electrons in atom can only have specific energy

(energy levels) 1,2,3,4,5,… 𝑅𝐸
𝐸 =− 2
𝑛
• Electrons change energy by going from one level
to another (transition)
• The energy is lost or gained as a photon.
 Spectral line production

electron jumps in energy levels in the

the H atom H atom
 Spectral line production
•Electron transitions
for an electron in the
hydrogen atom.

Δ 𝐸=− 𝑅 𝐸
( 1
2
1
− 2
𝑛 𝑓 𝑛𝑖 )
RE = 2.179 × 10-18 J
 Textbook: See also
Examples 7.4
Problem 3 Exercise 7.4 and 7.5

What is the frequency of the light

emitted when the electron in a
hydrogen atom undergoes a transition
from n = 6 to n = 3?

2. Use ΔE as energy to find ν

1. Find ΔE (ni is 6 and nf is 3)

c=2.998 x 108 m s-1

h=6.626 x 10-34 J s
RE=2.179 x 10-18 J
 Problem 3

What is the frequency of the light emitted

when the electron in a hydrogen atom
undergoes a transition from n = 6 to n = 3?

1. Find ΔE (ni is 6 and nf is 3)

c=2.998 x 108 m s-1

h=6.626 x 10-34 J s
RE=2.179 x 10-18 J
 Problem 3
2. Use ΔE as energy to find ν

ΔE is negative. This means the atom has lost energy

The photon will always have positive energy

c=2.998 x 108 m s-1

h=6.626 x 10-34 J s
RE=2.179 x 10-18 J
•Light is absorbed by an atom when the electron
goes to higher n. ΔE +ve.

•Light is emitted from an atom when the electron

goes to lower n. ΔE -ve.

•An electron is ejected when nf = ∞.

 Wavelength of particles

•Photons: use and

•DO NOT USE THESE EQUATIONS for particles like

electrons (only photons travel at the speed of
light, c)
The wavelength of a particle (that is NOT a
PHOTON) of mass, m (kg), and velocity, v (m/s),
is (de Broglie) :

h=6.626 x 10-34 J.s

 Textbook: See also
Examples 7.5
Problem 4 Exercise 7.6

What is the wavelength of an electron (mass

9.109 x 10-31kg) travelling at 30% c m s-1.

30
velocity= ×𝑐
100
30 8 −1
velocity= ×2.998 × 10 𝑚 𝑠 h
100 λ=
𝑚v
7 −1
¿ 8.994 ×10 𝑚 𝑠
c=2.998 x 108 m s-1
h=6.626 x 10-34 J s
RE=2.179 x 10-18 J
 Problem 4

What is the wavelength of an electron

(mass 9.109 x 10-31kg) travelling at 30% c
m s-1.
7 −1
velocity =8.994 × 10 𝑚 𝑠
h
λ=
𝑚v
h
− 34
6.626 ×10 J 𝑠 λ=
¿ 𝑚v
−31 7 −1
9.109 ×10 𝑘𝑔 × 8.994 ×10 𝑚 𝑠

−12 c=2.998 x 108 m s-1

¿ 8.088 × 10 𝑚 h=6.626 x 10-34 J s
RE=2.179 x 10-18 J
 Quantum Numbers and Atomic
Orbitals
• Electrons have wave properties
• Energy levels (1, 2, 3, …) only partly describe
what the electrons are doing.
• Electrons don’t go in a circular path around the
nucleus
• We say the electron is described by an atomic
orbital or wavefunction.
 Atomic orbitals
• An atomic orbital. " in the Bohr model: an orbit is
an electron's path around the nucleus.

• An orbital is a mathematical function with no direct

physical meaning.

• The orbital is the probability density.

• Electron density diagrams are sometimes called

electron cloud.

• The electron cloud is an imaginary picture of the

electron changing its position rapidly over time.
Quantum Numbers and Atomic
Orbitals
 QUANTUM NUMBERS

• Electrons in an orbitals ( an atomic orbitals) are

described by four quantum numbers.

• 1. Principal quantum number (n)- energy & size

• 2. Angular momentum quantum number (l) - shape

• 3. Magnetic quantum number (ml)– orientation

• 4. Spin quantum number (ms) - electron Spin

Quantum number is a number that specifies a property of

an orbital or an electron
 Principle quantum number (n)
• The principal quantum number (n) is a positive
integer (1, 2, 3…….).
• It indicates the energy level (shell).

• Shells are sometimes designated by the following

letters:
Letter K L M N
n 1 2 3 4
 Angular Momentum Quantum Number, l
• It is related to the shape.
• Sometimes is called azimuthal quantum number.
• Orbitals in given n (shell) can have different
shapes. Subshell.
• It can have values from 0, 1, 2, 3, . . . to a
maximum of (n – 1).

l 0 1 2 3 ...
Letter s p d f
n≥ 1 2 3 4
 Magnetic Quantum Number, ml

• Orientation of the orbital in the space around the

nucleus.
• Orbitals of a given n and l (energy and shape) but
different orientations.
• any value from –l to 0 to +l.
• The number of possible ml values equals the
number of orbitals, which is 2l + 1 for a given l
value.
• if l is 2, then there are five possible orientations:
• ml can be -2,-1,0,1 or 2
 s orbitals (l=0)

n=1

n=2

• l=0, ml=0
 p orbitals (l=1)

n=2

pz py px

n=
3

• l=1, ml= -1,0,+1

 d orbitals

n=
3

ml= ml=1 ml=2

0

n=4

• l=2, ml=-2,-1,0,+1,+2
 f orbitals (l=3)
n=3

ml=0 ml=1 ml=2

• l=3, ml=-3,-2,-1,0,+1,+2,+3
 Textbook: See also
Example 7.6
Problem 5 Exercise 7.7

• What values of l and ml are possible, for n=1,2,3,4,5

?
 Spin quantum number, ms

• Spin
• Electron spin
• either +1/2 or -1/2.
 Paramagnetic/Diamagnetic

• If an atom or a molecule has one or more

unpaired electrons it is paramagnetic (strongly
attracted to magnetic field)

• If an atom or a molecule has no unpaired

electrons it is diamagnetic (weakly repelled from
a magnetic field)
 Problem 6

• Which of the following are permissible sets of

quantum numbers?

n = 4, l = 4, ml = 0, ms = ½
n = 3, l = 2, ml = 1, ms = -½
n = 2, l = 0, ml = 0, ms = ³/²
n = 5, l = 3, ml = -3, ms = ½
 Electrons in Orbitals

•The Pauli exclusion principle

•no two electrons in one atom can have the same

four quantum numbers.

•one orbital can hold 2 electrons

 Electrons in Atoms

• An electron configuration is how electrons are

distributed in subshells (orbital).
• An orbital diagram shows how the orbitals are
occupied by electrons.
• The lowest-energy is called ground state.
• Anything else is an excited state.
• The maximum number of electrons in various
subshells is given in the following table.

Number of Maximum Number

• Subshell Orbitals of Electrons
• s (l=0) 1 2
• p (l=1) 3 6
• d (l=2) 5 10
• f (l=3) 7 14
 Electrons in Atoms

•An s subshell, 1 orbital, at most 2 electrons.

–l=0, ml=0
•A p subshell, 3 orbitals, at most 6 electrons.
•l=1, ml=-1,0,+1
•A d subshell, 5 orbitals, at most 10 electrons.
–l=2, ml=-2,-1,0,+1,+2
 Electrons in Atoms
•The building-up principle (or aufbau principle)
•Filling the orbitals from lowest to highest energy.
 1s
2s 2p
3s 3p 3d
4s 4p 4d 4f

5s 5p 5d 5f
6s 6p
6d
7s 7p

This results in the following order:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p,
6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
 Electrons in Atoms

• The complete electron configuration shows every subshell

explicitly.

•Br: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5

Building-Up Principle (Aufbau Principle)
• Building-up principle (or Aufbau principle), is a
scheme used to reproduce the electron
configurations of the ground states of atoms by
successively filling subshells with electrons in a
specific order (the building-up order).

• The Aufbau principle dictates that as protons are

added one by one to the nucleus to build up the
elements, electrons are similarly added to the
atomic orbitals
• Following the principle, the electron
configuration of an atom is obtained by
successively filling subshells in the following
order:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d,
6p, 7s, 5f

• The Hund’s rule state that when orbitals of equal

energy are available, the electron configuration of
lowest energy has the maximum number of
unpaired electrons with parallel spins.
The Energies of Subshells
• Example
2p6
2 = principal quantum #,
P = angular quantum # &
6 = # of electrons in the subshell or orbitals

Electron configuration for, aluminum, gallium

1s2 2s22p1 or [He]2s22p1

1s22s22p63s23p1 or [Ne]3s23p1

2 2 6 2 6 10 2 1 10 2 1
Noble-gas core, is the electron configuration of the
noble gas element that most nearly precedes the element
being considered.

an abbreviation in an atom's electron configuration

where the previous noble gas's electron configuration is
replaced with the noble gas's element symbol in brackets

The noble-gas core together with (n-1)d10 electrons is

often referred to as a pseudo-noble-gas core, because
these electrons usually are not involved in chemical
reactions
• An element with pseudo noble gas configuration
has 18 electrons in the outermost shell instead of
8.
• Write the noble gas core electron configuration of
the following
 11Na
 18Ar
 36Kr
 O2-
 Ca2+
PERIODIC TABLE & BLOCKS
 Valence Shell Configuration
• Electrons outside the noble gas core or the pseudo
noble gas core are called valence electrons.

• Distribution of valence electrons in the orbitals of

an atom is called valence shell configuration

• Ground state configuration for thallium;

81Tℓ ( Z= 81) is: [Xe]4f 14
5d10
6s2
6p1

• The valence shell configuration is: 6s26p1

 Diamagnetism and Paramagnetism
• Paramagnetic substances are those that contain net
unpaired spins and are attracted by a magnet. On the
other hand, if the electron spins are paired, or
antiparallel to each other, the magnetic effects cancel
out
• Diamagnetic substances do not contain net unpaired
spins and are slightly repelled by a magnet.
• If the two electrons in the 1 s orbital of a helium atom
had the same, or parallel, spins , their net magnetic
fields would reinforce each other Such an
arrangement would make the helium gas paramagnetic
 ANOMALIES IN ELECTRON CONFIGURATION
• The electron configuration of chromium ( Z=24) is [Ar]4
s13d5 and not [Ar]4s2 3d4, as we might expect.
• Similarly for copper, whose electron configuration is [Ar]4
s1 3d 10 rather than [Ar]4 s2 3d9 .
• The reason for these irregularities is that a slightly
greater stability is associated with the half-filled (3d 5) and
completely filled (3d10 ) subshells.
• Electrons in the same subshell (in this case, the d
orbitals) have equal energy but different spatial
distributions. Consequently, their shielding of one
another is relatively small, and the electrons are more
strongly attracted by the nucleus when they have the 3d 5
 ANOMALIES IN ELECTRON CONFIGURATION

• the 5d and 4f orbitals are very close; for lanthanum

4f is slightly higher in energy than 5d . Thus,
lanthanum’s electron configuration is [Xe]6s25d1 and
not [Xe]6s24f1.
• After the 4f subshell is completely filled, the next
electron enters the 5d subshell of lutetium. Note
that the electron configuration of gadolinium
( Z=64) is [Xe]6s24f75d1 rather than [Xe]6s24f8 . Like
chromium, gadolinium gains extra stability by
having a half-filled subshell (4f7).
Arrangement of Elements in the Periodic
Table
 Periodic trends in physical properties
• Some of the physical properties to be
discussed include:
 Atomic radius
 Ionic radius
 Ionization energy
 Electron affinity
1. Atomic Radius

• Atomic Radius is one half the distance between the

two nuclei in two adjacent metal atoms or in a
diatomic molecule .

• Atomic radius generally increases in a group from

top to bottom. Even though the nuclear charge
increase down the group, the atoms get larger as a
result of the increasing n value.
• Atomic radius generally decreases in a period
from left to right. Because outer electrons
shield each other poorly, Zeff on the outer
electrons rises significantly, and so they are
pulled closer to the nucleus.

• The diagram below shows the the atomic

radius in pm
EFFECTIVE NUCLEAR CHARGE
• Consider element number 4 which is beryllium, 4Be.
• The atom of beryllium has 4 protons therefore a
nuclear charge of 4+.
• Its electronic configuration should be 2.2.
• The atom has two shells and 2 electrons in each
shell.
 EFFECTIVE NUCLEAR CHARGE conti
• Attraction felt by each electron due to the nuclear
charge is partially reduced by
 the mutual repulsion of electrons in the same shell,
 blocking of the nuclear attractive force by inner
shell electrons.
• Consequently in 4Be, the nuclear charge (residual
attractive force for the valence shell electrons)
seems to carry a charge of less than 4+.
 EFFECTIVE NUCLEAR CHARGE
• Actual force of attraction felt by the valence shell
electrons is referred to as effective nuclear charge,
Zeff
• Zeff is given by:
Zeff = Z - 
• where Z is the actual nuclear charge,  is known as
the shielding constant
• or screening constant which constitute all electrons
in the inner shell
 EFFECTIVE NUCLEAR CHARGE
• Note the following important points about
shielding:
 Electrons in a given shell are shielded by electrons
in the inner shell(s)
 Inner filled shells shield outer electrons more
efficiently than electrons in the same shell shield
one other.
• There4 electrons in the same shell do not shield
each other.
• Remember Zeff = Z-σ, where Z is the nuclear charge
& σ is the shielding or screening constant (total
number of inner electrons.)
• Let us calculate the Zeff for all the Period 2 elements.

• For 3Li, Zeff = 3-2 = 1+ Be, Zeff = 4-2 = 2+

4

5B, Zeff = 5-2 = 3+ C, Zeff = 6-2 = 4+

6

7N, Zeff = 7-2 = 5+ O, Zeff = 8-2 = 6+

8

9F, Zeff = 9-2 = 7+ 10Ne, Zeff = 10-2 =8+

GRAPH OF ATOMIC RADIUS Vs ATOMIC NUMBER
 EXERCISE

1. Arrange the following elements in order of

increasing atomic radii: Cs, F, K, Cℓ
2. IONIC RADIUS
• Ionic radius is the radius of a cation or an anion
• Would you expect positive ions (cations) / negative
ions (anions) to be larger or smaller than their
corresponding atoms?
• Calculate and compare Zeffs for 7N & 7N3-
Zeffs for 7N = 7-2 = 5+ for 5 ē ( = 1+/ ē).
Zeffs for 7N = 7-2 = 5+ for 8 ē ( = 0.625+/ ē).
• There is therefore reduction in the attractive force
per electron.
• In addition, there is increase in electron-electron
repulsive forces which also contributes to the
ISOELECTRONIC
• Means atoms or ions with the same # of electrons
• Arrange the following ions: (i) N3- , O2-, F- in order of increasing
size.
• Calculate Zeff for each since they are in the same Period and are
isoelectronic:
N3- = 7-2 = 5+; O2- = 8-2 = 6+; F- = 9-2 = 7+
• Since each of the Zeff is for 8 ēs, then the Zeff/electron increases
from N3- , O2-, F-.
• Therefore the order of increasing size is:
F- < O2- < N3-.
• Therefore for iso-electronic anions, size increases as “negative
charge” of the anions increase.
• Why?
3. IONIZATION ENERGY (IE)
• Ionization Energy is the energy (in kJ) required for
the complete removal of 1 mol of electrons from 1
mol of gaseous atoms or ions

• The first ionization energy (IE1, ) removes an

outermost electron (highest energy sublevel) from
the gaseous atom:
• The second ionization energy (1E2) removes a
second electron. This electron is pulled away from a
positively charged ion, so 1E2 is always larger than
IE1 , Ion+ (g)  ion2+(g) + e- E = IE2 (always > lEI)
IONIZATION ENERGY & ATOMIC NUMBER
 IONIZATION ENERGY cont
• IE generally increases across a period : the orbital's
n value stays the same, so Zeff increases and atomic
size decreases. the attraction between nucleus and
outer electrons increases, which makes an electron
harder to remove
• IE generally decreases down a group: it is easier to
remove an outer electron from an element in
Period 6 than Period 2
• IE, is important in determining whether atoms of
the elements will prefer to form ionic or molecular
compounds.
• IONIZATION ENERGY cont…

• The removal of electrons from a gaseous state takes

place in steps depending on number of ēs in the
valence shell.
• Thus IE1, IE2, IE3 may occur as during the formation
of Aℓ3+. Normally, huge differences in IEs occur if the
subsequent (i.e. next) ionisation involves an inner
shell electron
• The amount of energy required to remove the first
electron from the gaseous atom is called first
ionization energy
• IONIZATION ENERGY cont…..

• Thus ionisation energies always increase in the following

order: IE1 < IE2 < IE3 Give reason?
• Metals have relatively low IE values & consequently valence
electrons are easily removed from metals
• Non-metals have relatively high IE values & consequently
valence electrons are difficult to remove from non-metals.
• In addition, IEs progressively increase across the Period due
to increase Zeff.
• Furthermore, IEs progressively decreases down the Group.
• Why??
• Due to increase in atomic radius
3.The electron affinity (EA)
• The electron affinity (EA) is the energy change (in
kJ) accompanying the addition of 1 mol of electrons
to 1 mol of gaseous atoms or ions.
• energy is released when the first electron is added
because it is attracted to the atom's nuclear charge.
• The second electron affinity (EA2), is always positive
because energy must be absorbed in order to
overcome electrostatic repulsions and add another
electron to a negative ion.
• Electron affinities are highest for elements near
fluorine, particularly the halogens.
ELECTRON AFFINITIES
 moving across the period, the EA for an atom to
attract a foreign ē(s) increases. Due to increse Zeff
• By convention, EA is assigned a +ve value if energy is absorbed during

the EA where the produced anion has higher energy (enthalpy) than

both the neutral atom and the electron (i.e ΔH is +ve).

• Conversely, EA is assigned a –ve value if energy is released to the

surrounding during the EA where the produced anion has lower energy

(enthalpy) than both the neutral atom and the electron (i.e ΔH is -ve).
 ELECTRON AFFINITY cont…
• The more –ve values implies the atoms have higher the
tendency to accept foreign ē(s) and form stable anions.
• Therefore elements that have no affinity (natural
tendency) to accept an ē(s) have an EA of zero (0).
• Which elements have zero EAs?
• Noble gases.
• What would be both the sign & magnitude of EA of
elements with high values of Zeff?
-ve and large.
• Why??
They have high tendency to attract extra ēs (EA)
 ELECTRON AFFINITY cont…
• O(g) + ē → O-(g), EA = -142 kJ/mol and the
• EA for O-(g) + ē → O2-(g) = + 780 kJ/mol
Why?
• Because both –vely charged species are
forced to combine & Such a process is an
unfavourable one !!!
CHEMICAL PROPERTIES & PERIODIC TABLE
READING ASSIGNMENT : CHEMICAL PROPERTIES OF
GROUP 1, 2 & 17 USING THE IUPAC SYSTEM
EMPHASIS SHOULD BE ON CHEMICAL EQUATIONS