BASIC CHEMISTRY FOR ENGINEER

Electronic structure

Shishir Kanti Pramanik, PhD

Professor
Department of Chemistry, SUST

Dept. of Chemistry, SUST

CHE 05311101C BASIC CHEMISTRY FOR ENGINEER (CEE)
3 Hours/Week, 3.0 Credits

➢ To understand the structures, properties and applications od

atom, molecules and chemical compounds

1. Electronic Structure: Quantum theory, atomic spectrum of hydrogen

and the Bohr model, Quantum numbers, Concept of Energy levels and
atomic orbital, Electronic configuration, Chemical bonding and molecular
structure.
2. The periodic Table: Development of the periodic table, Electron
arrangements and the periodic table, Summarized chemical properties of
s-block, p-block and d-block elements.
3.Chemical formulas and equations: Types of formulas, Percent
composition from formula, Formulas from experiment, Formulas of ionic
compounds, Names of compounds, Mass relations in reactions, Limited
reactant and theoretical yield. Concept of mole, Solution: Different
concentration units.
4. Acids and Bases: Theories and Modern definition of acids and bases,
Dissociation constant, strength, pH, Buffer solution etc.

2
Dept. of Chemistry, SUST
5. Introduction to Chemical Kinetics: Rate laws, rate constant,
equilibrium constant, order of reaction etc.

5. Fundamentals of Organic Chemistry:

A. Introduction, Classification, Nomenclatures, preparations and
Properties (Physical & Chemical) of (i) Aliphatic and aromatic
hydrocarbons, (ii) Aldehydes and ketones, (iii) Carboxylic acids and (iv)
Alcohols and phenols (v)Carbohydrates (mono- , disaccharides)
B. Chemistry of Fuels (Hydrocarbon, Hydrogen)

3
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
Atomic Structure • Every matter consists of basis entities called elements.
• Each element is composed of smallest particles called
atom.
• Greek Philosopher Democritus in 460 BC first suggest
the existence of atoms
• Suggested world was made of two things – empty
space and “atoms”
• Atoms – Greek word for uncuttable
• 2 Main ideas
• Atoms are the smallest possible particle of matter
• There are different types of atoms for each material
• Atom consists positively charged nucleus at the center
and negatively charged electrons revolving around it
• Radius of atom 10-10 m
• Radius of nucleus 10-15 m
• Nucleus consists of protons and neutrons
• Most of the mass of atom is possessed by nucleus
4
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
John Dalton’s Atomic Theory (1803 AD)
suggested that all matter was made up of tiny spheres that were

able to bounce around with perfect elasticity and called them Atom

• All matter is made of atoms, they are indestructible.

• Atoms cannot be broken down into smaller parts

• All atoms of one element are identical in their physical and chemical properties.

• Atoms of different elements differ in their physical and chemical properties.

• Atoms of different elements combine in simple whole-number ratios to form

molecules

• Chemical reaction consist of the combination or rearrangement of atoms

5
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

16 X + 8Y 8 X2Y

Limitations of Dalton’s Atomic Theory

• Why and how do atoms combine together to form compound atom/molecules ?
• The nature of forces which hold atoms together in compound atoms
• Why atoms cannot exist in free state and why compound atoms can exist freely?

6
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
Joseph John Thompson (1898)

▪ Discovered the electron (negative particles within the atom)

▪ He was the first scientist to show the atom was made of even
smaller things
▪ Used the Cathode ray tube to discover electrons

Voltage source
+

-
-
7
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Thomson’s “Plum Pudding” Atom Model (1904)

• Negative charge particles are evenly

scattered throughout an atom with
positively charged mass of matter.
• Similar to that of chocolate chip ice-cream
• Later proved to be incorrect

Limitations
▪ It could not explain the result of scattering experiment explained by the
Rutherford experiment
▪ It did not have any experimental evidence in its support.

8
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
Rutherford’s atomic model: The nuclear atom

Discovered the nucleus of a gold atom with his “gold foil” experiment

Having known that atom contains electrons and a positive ion, Rutherford
proceeded to perform experiments to know as to how and where these
were located in the atom.
In 1909 Rutherford and Marsden performed their historic Alpha Particle-
Scattering Experiment, using the apparatus illustrated in Fig. 1.6.

9
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
They directed a stream of very highly energetic α-particles from a
radioactive source against a thin gold foil provided with a circular
fluorescent zinc sulphide screen around it. Whenever an α-particle struck
the screen, a tiny flash of light was produced at that point.

Rutherford and Marsden noticed that most of the α-particles passed straight
through the gold foil and thus produced a flash on the screen behind it. This
indicated that gold atoms had a structure with plenty of empty
space. To their great astonishment, tiny flashes were also seen on
other portions of the screen, some time in front of the gold foil. This
showed that gold atoms deflected or ‘scattered’ α-particles through
large angles so much so that some of these bounced back to the source.
Based on these observations, Rutherford proposed a model of the atom
which is named after him. This is also called the Nuclear Atom. According
to it :
10
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
Using J.J Thomson’s Plum Pudding atomic model, Rutherford predicted
the alpha particles would pass straight though the gold foil. That’s not
what happened.

11
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
Gold Foil Experiment Results
most alpha particles go straight through the
gold foil
A few alpha particles are sharply deflected

12
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

(1) Atom has a tiny dense central core or the nucleus which contains
practically the entire mass of the atom, leaving the rest of the atom
almost empty.
(2) The entire positive charge of the atom is located on the nucleus,
while electrons were distributed in vacant space around it. It was due to
the presence of the positive charge on the nucleus that α-particle (He2+) were
repelled by it and scattered in all directions.

(3) The electrons were

moving in orbits or closed
circular paths around the
nucleus like planets around
the sun.

13
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Rutherford’s Conclusion

• The atom is mostly empty space.

• There is a small, dense center with a positive

charge Which is nucleus.

• The mass of atom and its whole positive charge

are concentrated at the center of the atom in a
nucleus.

14
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Rutherford’s drawback

Regarding stability of atom

▪ Electron revolving around the nucleus have centripetal acceleration
▪ According to electrodynamics, the accelerated charged particles
radiate energy in the form of electromagnetic waves and should be
continuously radiated by the revolving electrons.
▪ Due to continuous loss of energy of electron, the radii of their orbits
should be continuously decreasing and ultimately the electron should
fall into the nucleus . Thus the atom cannot remain stable.
▪ Rutherford’s model also failed to explain the line spectrum.

15 Dept. of Chemistry, SUST

 ATOMIC STRUCTURE

Atom – smallest particle of an element that can

exist alone
Atoms are composed of
-protons – positively charged particles
-neutrons – neutral particles
-electrons – negatively charged particles
Protons and neutrons are located in the nucleus.
Electrons are found in orbitals surrounding the
nucleus.

16
Dept. of Chemistry, SUST
 ATOMIC STRUCTURE

HELIUM ATOM
proton Shell

+N -
N +
-

electron neutron

Every different atom has a characteristic number of protons in the

nucleus.
atomic number = number of protons
Atoms with the same atomic number have the same chemical
properties and belong to the same element.
17
Dept. of Chemistry, SUST
 ATOMIC STRUCTURE
Each proton and neutron has a mass of approximately 1 dalton.

The sum of protons and neutrons is the atom’s atomic mass.

Isotopes – atoms of the same element that have different atomic

mass numbers due to different numbers of neutrons.
Atomic number
the number of protons in an atom 2
Atomic mass
the number of protons and neutrons
in an atom
4 He
number of electrons = number of protons
18
Dept. of Chemistry, SUST
 ATOMIC STRUCTURE
ATOMIC NUMBER (Z) = number of protons in nucleus
MASS NUMBER (A) = number of protons + number of neutrons
= atomic number (Z) + number of neutrons
ISOTOPS are atoms of the same element (X) with different numbers of
neutrons in the nucleus
Mass Number A
ZX
Element Symbol
Atomic Number

1 2 3
1H 1H (D) 1H (T)
235 238
92 U 92 U
19
Dept. of Chemistry, SUST
ATOMIC STRUCTURE

20
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Niels Bohr (1913): studied under Rutherford at the Victoria

University in Manchester.

Rutherford’s nuclear model simply stated that atom had a nucleus and the
negative electrons were present outside the nucleus. It did not say anything
as to how and where those electrons were arranged. It also could not
explain why electrons did not fall into the nucleus due to electrostatic
attraction.

Bohr refined Rutherford's idea by adding that the electrons were

in orbits. Rather like planets orbiting the sun. With each orbit only
able to contain a set number of electrons.

21
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
In 1913 Niels Bohr proposed a new model of atom which explained some of
these things and also the emission spectrum of hydrogen. Bohr’s theory was
based on Planck’s quantum theory and was built on the following
postulates based on the “Theory of electrons orbiting around the nucleus”
Postulates of Bohr’s Theory
Postulate of energy levels
(1) An atom has a number of stable orbits in which an electron move around the
nucleus in concentric circular orbits. These orbits are referred to as “energy
levels”.

(2) While revolving in stable orbits, the electron do not radiate energy in spite of
their acceleration toward the center of the orbits. The electron in the orbits
possess an integral multiple of quantum of energy, i.e., hγ

(3) Electrons in each fixed orbits have a definite energy called stationary energy
and are at a fixed distance from the nucleus. The energy level are numbered
as 1, 2, 3, etc. or designed as K, L, M, etc as the distance from the nucleus
increases.

22 Dept. of Chemistry, SUST

 HISTORY OF THE ATOM
(4) An electron can move from one energy level to another by quantum
or photon jumps only.

When an electron resides in the orbit

which is lowest in energy (which is also
closest to the nucleus), the electron is
said to be in the ground state. When an
electron is supplied energy, it absorbs
one quantum or photon of energy and
jumps to a higher energy level. The
electron then has potential energy and is
said to be in an excited state.

(5) The angular momentum (mvr) of an electron orbiting around the nucleus
is an integral multiple of Planck’s constant divided by 2π.

23
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
h
Angular momentum , mvr = n
2
where m = mass of electron, v = velocity of the electron, r = radius of the orbit ; n = 1, 2, 3,
etc., and h = Planck’s constant.

Postulate of radiation

▪ An atom radiate energy as light only when electron jump from higher energy level to
another lower energy giving definite spectral line in emission spectra.

▪ Jump an electron from lower to higher energy level by absorption of energy giving dark
lines.

▪ The quantity of energy radiated or absorbed is equal to the difference between the
energies the atom possessed before and after the electron changed orbits.

▪ The energy radiated, E2-E1 = hγ Where, E2> E1 ; h is Planck’s constant (6.62 x 10-27
erg/sec); γ is frequency of radiation

24
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Limitation of Bohr’s postulates

▪ No explanation for the spectra of multi electron system. e,g., He, Li

▪ No explanation of fine spectrum of atoms
▪ No explanation for Zeeman and stark effect ( effect of electric and
magnetic fields on the spectral
▪ When magnetic field is applied on an atom, it usually observed
spectral lines split. This effect is known as Zeeman’s effect.
▪ Spectral line also get split in presence of electric field. This effect is
known as Stark effect.

25
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Calculation of radius of a Bohr orbit:

Consider an electron of charge e revolving
around a nucleus of charge Ze, where Z is
the atomic number and e the charge on
a proton.
Let m be the mass of the electron, r the
radius of the orbit and ν the tangential
velocity of the revolving electron. The
electrostatic force of attraction between
the nucleus and the electron
(Coulomb’s law),
Ze  e
=
r2
mv 2
The centrifugal force acting on the electron =
r
26
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM
Bohr assumed that these two opposing forces must be balancing
each other exactly to keep the electron in orbit. Thus,
Ze  e mv 2
2
=
r r
For hydrogen Z = 1, therefore,

e 2 mv 2
2
= (1)
r r
e2
or , = mv 2 (2)
r
According to one of the postulates of Bohr’s theory, angular momentum of
the revolving electron is given by the expression
h
Angular momentum , mvr = n
2 Dept. of Chemistry, SUST
27
 HISTORY OF THE ATOM

nh
or , v = (3)
2 mr
Substituting the value of ν in equation (2)
2
Since the value of h, m and e had
e2  nh  been determined experimentally,
or , = m 
r  2mr  substituting these values in (4), we
have
e2
or , r = r = n2 × 0.529 × 10–8 cm (5)
mn 2 h 2
4 2 m 2 r 2 For n=1 for hydrogen (Z=1), The radius
of the first orbit r,= 0.529× 10-8 cm Or
n2h2 0.53 Ao
or , r = (4)
4 2 me 2

28 Dept. of Chemistry, SUST

 HISTORY OF THE ATOM
Calculation energy
The total energy E of an electron is equal to the sum of the kinetic energy(K.E.)
and the potential energy (P.E.). The kinetic energy = 1/2 mv2 and the potential
energy of an electron of charge Z.e at a distance r from the nucleus is given,
P.E. = ̶ Ze2/r.

The total energy E of an electron in any orbit is:

E = K.E. + P.E.
𝑚𝑣2 𝑍𝑒2
E= ̶
2 2
𝑟 2
𝑚𝑣 𝑍𝑒
Since, = 2
𝑟 𝑟

𝑍𝑒2 𝑍𝑒2 𝑍𝑒2

Therefore, E = ̶ = ̶ ……………(1)
2𝑟 𝑟 2𝑟

Substituting r value ( r = n2h2/4π2m.Z.e2 )in the equation

2π2𝑍2𝑒4𝑚 13.6
E= ̶ = ̶ electron volts
𝑛2ℎ2 𝑛2
29
Dept. of Chemistry, SUST
HISTORY OF THE ATOM

30
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

The Bohr Model of the Atom According to Bohr’s postulate,

when an electron passes from
one orbit to another lower energy,
radiate of energy E2-E1 = hγ,
where E2> E1

2π2𝑍2𝑒4𝑚 1 1
E2-E1 = hγ = ( 2 ̶ )
ℎ2 𝑛1 𝑛22

Since, γ = γ.c
2 2 4
γ = 2π 𝑍 𝑒 𝑚 1 1
( 2 ̶ )
ℎ3 𝑛1 𝑛22

1 2π2𝑍2𝑒4𝑚 1 1
= ( 2 ̶ )
λ ℎ3 𝑛1 𝑛22
1 1 1
= R( 2 ̶ )
λ 𝑛1 𝑛22
R is Rydberg Constant
31
Dept. of Chemistry, SUST
 HISTORY OF THE ATOM

Origin of the Spectral line

γ = 1 1
R( ̶ )
𝑛12 𝑛22

Lyman series: n1 =1, n2 =2,3,4,5..

Happen in the ultraviolet region

Balmer series: n1 =2, n2 =3,4,5..

Happen in the visible region

Paschen series: n1 =3, n2 =4,5..

Happen in the infrared region

Backett series: n1 =4, n2 =5..

Happen in the infrared region

32
Dept. of Chemistry, SUST
HISTORY OF THE ATOM

33
Dept. of Chemistry, SUST
HISTORY OF THE ATOM

34
Dept. of Chemistry, SUST
HISTORY OF THE ATOM

35
Dept. of Chemistry, SUST
 Electronic Structure
Quantum Numbers and Atomic Orbitals
An atomic orbital is specified by four quantum numbers that are necessary to
describe an electron orbit in an atom in terms of i) size, ii) shape, iii) orientation in
space and iv) direction of spin of electron in its axis.
▪ Principal quantum number (n) – represents any particular circular orbit.
Mean size of the electron orbit. If n=1, it represent first energy level; n=2
represents the second energy level and so on.

▪ Subsidiary quantum (l)- describe the shapes of the electron’s orbit. The
term l may have values from o to n-1. For example, if n = 1, the only
possibility is l = 0. If n = 2, then l can be 0 or 1.

▪ Magnetic t quantum number (m)- explain the orientation of electronic orbit

in space particularly under the influence of an applied magnetic field. m can
have values from –l to +l including 0. For example, when n=1, then l=0 and
m=0 only. When n=2, l=0,1 therefore when l=0, m=0 and for l=1, m= -1,0,+1
36
Dept. of Chemistry, SUST
 Electronic Structure
The three quantum numbers are actually giving the energy of the electron in the
orbital and a fourth quantum number is needed to describe a property of electrons
called spin. The spin can be clockwise or counterclockwise.
▪ The spin quantum number (s)- represents the direction electron spin about
their axis. it can have the values + ½ or - ½ .
Table Summary of Quantum Numbers of Electrons in Atoms
Name Symbol Permitted Values Property

principal n positive integers(1,2,3,…) orbital energy (size)

angular l integers from 0 to n-1 orbital shape (The l values 0,
momentum 1, 2, and 3 correspond to s,
p, d, and f orbitals,
respectively.)
magnetic m integers from -l to 0 to +l orbital orientation

spin s +1/2 or -1/2 direction of e- spin

37 Dept. of Chemistry, SUST

 Electronic Structure

ORBITALS
ORBITAL SHAPE OCCURRENCE
s spherical one in every principal level
p dumb-bell three in levels from 2 upwards
d various five in levels from 3 upwards
f various seven in levels from 4 upwards

SHAPES OF ORBITALS

s orbitals (sperical)
38 Dept. of Chemistry, SUST
 Electronic Structure
Differences between a 1s and a 2s orbital

The orbital occupied by the hydrogen electron is called a 1s

orbital. The "1" represents the fact that the orbital is in the
energy level closest to the nucleus. The "s" tells you about
the shape of the orbital. s orbitals are spherically symmetric
around the nucleus - in each case, like a hollow ball made of
rather chunky material with the nucleus at its centre.

The orbital on the left is a 2s orbital. This is similar to a 1s

orbital except that the region where there is the greatest
chance of finding the electron is further from the nucleus -
this is an orbital at the second energy level.

39
Dept. of Chemistry, SUST
 Electronic Structure
SHAPES OF ORBITALS d orbitals

p orbitals

• dumb-bell shaped
• various shapes
• three occur in energy levels except the
• five occur in energy levels except
first
the first and second

40
Dept. of Chemistry, SUST
 Electronic Structure
ORBITALS
An orbital is... a region in space where one is likely to find an electron.
Orbitals can hold up to two electrons as long as they have opposite spin; this
is known as PAULI’S EXCLUSION PRINCIPAL.

41
Dept. of Chemistry, SUST
Electronic Structure

42
Dept. of Chemistry, SUST
Electronic Structure

43
Dept. of Chemistry, SUST
 Electronic Structure
Electron configuration : LEVELS AND SUB-LEVELS
PRINCIPAL
ENERGY energy gap between successive levels
LEVELS got increasingly smaller as the levels
4 got further from the nucleus.
INCREASING ENERGY / DISTANCE FROM NUCLEUS

1
44
Dept. of Chemistry, SUST
 Electronic Structure
LEVELS AND SUB-LEVELS
PRINCIPAL SUB LEVELS
ENERGY main energy levels were split into sub
LEVELS levels.
4 Level 1 was split into 1 sub level
INCREASING ENERGY / DISTANCE FROM NUCLEUS

Level 2 was split into 2 sub levels

Level 3 was split into 3 sub levels

3 Level 4 was split into 4 sub levels

1
45
Dept. of Chemistry, SUST
 Rules and principles

Heisenberg’s uncertainty principle:

“You cannot determine the position and momentum of an electron at the same
time.”
This means that you cannot say exactly where an electron is.

46
Dept. of Chemistry, SUST
 Rules and principles

The aufbau principle

“Electrons are filled into atomic orbitals in the increasing order of orbital energy
level. According to the Aufbau principle, the available atomic orbitals with the lowest
energy levels are occupied before those with higher energy levels..”

Pauli’s exclusion principle

“No two electrons can have the same four quantum numbers.”
Two electrons can go in each orbital, providing they are of opposite spin.

Hund’s rule of maximum multiplicity”

“When in orbitals of equal energy, electrons will try
to remain unpaired.”
Placing two electrons in one orbital means that, as
they are both negatively charged, there will be
some electrostatic repulsion between them.
Placing each electron in a separate orbital reduces
the repulsion and the system is more stable.

47
Dept. of Chemistry, SUST
 Rules and principles

ORDER OF FILLING ORBITALS

PRINCIPAL SUB LEVELS
ENERGY
LEVELS 4f

INCREASING ENERGY / DISTANCE FROM NUCLEUS

4d
4
4p
4s

3d
3 3p
3s

2p
2 Orbitals are not filled in numerical order because
2s
the principal energy levels get closer together as
you get further from the nucleus. This results in
overlap of sub levels. The first example occurs
1 1s
when the 4s orbital is filled before the 3d orbitals.

48
Dept. of Chemistry, SUST
 Rules and principles
ORDER OF FILLING ORBITALS
PRINCIPAL SUB LEVELS
ENERGY PRINCIPAL SUB LEVELS
LEVELS 4f ENERGY HOW TO

INCREASING ENERGY / DISTANCE FROM NUCLEUS

4d LEVELS 4f REMEMBER ...
4 4d
4p 4 THE FILLING ORDER
4s 4p
3d 1s
3d 4s
2s 2p
3 3p 3 3p
3s 3s 3p 3d
3s
4s 4p 4d 4f
2p 5s 5p 5d 5f
2p 2
2 2s
2s 6s 6p 6d
7s 7p

1 1s
1 1s
Orbitals are not filled in numerical order because the principal energy levels get
closer together as you get further from the nucleus. This results in overlap of sub
levels. The first example occurs when the 4s orbital is filled before the 3d orbitals.
49
Dept. of Chemistry, SUST
 Rules and principles

Diagonal rule

HOW TO
REMEMBER ... There's a simple rule known as the diagonal
THE FILLING ORDER rule. The diagonal rule states that:
1s
2s 2p
3s 3p 3d Electrons fill orbitals in order of increasing
4s 4p 4d 4f "quantum number sum" (n + ℓ).
5s 5p 5d 5f
6s 6p 6d
When two orbitals share the same quantum
7s 7p
number sum, they will be filled in order of
increasing n.

50
Dept. of Chemistry, SUST
 Rules and principles

THE ‘AUFBAU’ PRINCIPAL

4f This states that…
4d “ELECTRONS ENTER THE
4 LOWEST AVAILABLE
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p ENERGY LEVEL”

3d The following sequence will

show the ‘building up’ of the
4s
electronic structures of the
3 3p first 36 elements in the
periodic table.
3s
Electrons are shown as half
headed arrows and can spin
in one of two directions
2p or
2
2s
s orbitals
p orbitals
1 1s d orbitals

51
Dept. of Chemistry, SUST
 Rules and principles

THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
HYDROGEN
4d
4 1s1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Hydrogen atoms have one
3d electron. This goes into a
4s vacant orbital in

3 3p

3s
The lowest available
energy level.
2p
2
2s
‘Aufbau’
Principle

1 1s

52
Dept. of Chemistry, SUST
 Rules and principles
THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
HELIUM
4d
4 1s2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Every orbital can contain 2
3d electrons, provided the
4s electrons are spinning in
opposite directions. This is
3 3p based on...
3s PAULI’S EXCLUSION
PRINCIPLE
The two electrons in a
2p helium atom can both go in
2 the 1s orbital.
2s

1 1s ‘Aufbau’
Principle
53
Dept. of Chemistry, SUST
 Rules and principles
THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
LITHIUM
4d
4 1s2 2s1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
1s orbitals can hold a
3d maximum of two electrons
4s so the third electron in a
lithium atom must go into
3 3p the next available orbital of
higher energy. This will be
3s
further from the nucleus in
the second principal
energy level.
2p
2 The second principal level
2s has two types of orbital (s
and p). An s orbital is
lower in energy than a p.

1 1s ‘Aufbau’
Principle
54
Dept. of Chemistry, SUST
 Rules and principles

THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
BERYLLIUM
4d
4 1s2 2s2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Beryllium atoms have four
3d electrons so the fourth
4s electron pairs up in the 2s
orbital. The 2s sub level is
3 3p now full.
3s

2p ‘Aufbau’
2
Principle
2s

1 1s

55
Dept. of Chemistry, SUST
 Rules and principles

THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
BORON
4d
4 1s2 2s2 2p1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
As the 2s sub level is now
3d full, the fifth electron goes
4s into one of the three p
orbitals in the 2p sub level.
3 3p The 2p orbitals are slightly
higher in energy than the
3s
2s orbital.

2p ‘Aufbau’
2
Principle
2s

1 1s

56
Dept. of Chemistry, SUST
 Rules and principles

THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
CARBON
4d
4 1s2 2s2 2p2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The next electron in
3d doesn’t pair up with the
4s one already there. This
would give rise to
3 3p repulsion between the
similarly charged species.
3s
Instead, it goes into
another p orbital which
means less repulsion,
2p lower energy and more
2 stability.
2s

HUND’S RULE
OF
1 1s
MAXIMUM MULTIPLICITY

57
Dept. of Chemistry, SUST
 Rules and principles
THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
NITROGEN
4d
4 1s2 2s2 2p3
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Following Hund’s Rule,
3d the next electron will not
4s pair up so goes into a
vacant p orbital. All three
3 3p electrons are now
unpaired. This gives less
3s
repulsion, lower energy
and therefore more
stability.
2p
2
2s

HUND’S RULE
OF
1 1s
MAXIMUM MULTIPLICITY

58
Dept. of Chemistry, SUST
 Rules and principles

THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
NEON
4d
4 1s2 2s2 2p6
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The electrons continue to
3d pair up with those in the
4s half-filled orbitals. The 2p
orbitals are now
3 3p completely filled and so is
the second principal
3s
energy level.
In the older system of
2p describing electronic
2 configurations, this would
2s have been written as 2,8.

1 1s

59
Dept. of Chemistry, SUST
 Rules and principles

THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
SODIUM - ARGON
4d
4
INCREASING ENERGY / DISTANCE FROM NUCLEUS

Na 1s2 2s2 2p6 3s1

4p
Mg 1s2 2s2 2p6 3s2
3d
4s Al 1s2 2s2 2p6 3s2 3p1

3 3p Si 1s2 2s2 2p6 3s2 3p2

3s P 1s2 2s2 2p6 3s2 3p3

S 1s2 2s2 2p6 3s2 3p4
Cl 1s2 2s2 2p6 3s2 3p5
2p
2 Ar 1s2 2s2 2p6 3s2 3p6
2s
Remember that the 3p
configurations follow Hund’s
1 Rule with the electrons
1s
remaining unpaired to give
more stability.
60
Dept. of Chemistry, SUST
H Rules and principles 1s1
ELECTRONIC
He 1s2
CONFIGURATIONS
Li 1s2 2s1
OF ELEMENTS 1-30
Be 1s2 2s2
B 1s2 2s2 2p1
C 1s2 2s2 2p2
N 1s2 2s2 2p3
O 1s2 2s2 2p4
F 1s2 2s2 2p5
Ne 1s2 2s2 2p6
Na 1s2 2s2 2p6 3s1
Mg 1s2 2s2 2p6 3s2
Al 1s2 2s2 2p6 3s2 3p1
Si 1s2 2s2 2p6 3s2 3p2
P 1s2 2s2 2p6 3s2 3p3
S 1s2 2s2 2p6 3s2 3p4
Cl 1s2 2s2 2p6 3s2 3p5
Ar 1s2 2s2 2p6 3s2 3p6
K 1s2 2s2 2p6 3s2 3p6 4s1
Ca 1s2 2s2 2p6 3s2 3p6 4s2
Sc 1s2 2s2 2p6 3s2 3p6 4s2 3d1
Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2
V 1s2 2s2 2p6 3s2 3p6 4s2 3d3
Cr 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Mn 1s2 2s2 2p6 3s2 3p6 4s2 3d5
Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Co 1s2 2s2 2p6 3s2 3p6 4s2 3d7
Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d8
Cu 1s2 2s2 2p6 3s2 3p6 4s1 3d10
Zn 1s2 2s2 2p6 3s2 3p6 4s2 3d10
61
Dept. of Chemistry, SUST
 Rules and principles
ELECTRONIC CONFIGURATION OF IONS
• Positive ions (cations) are formed by removing electrons from atoms
• Negative ions (anions) are formed by adding electrons to atoms
• Electrons are removed first from the highest occupied orbitals (EXC. transition metals)

SODIUM Na 1s2 2s2 2p6 3s1 1 electron removed from the 3s orbital
Na+ 1s2 2s2 2p6

CHLORINE Cl 1s2 2s2 2p6 3s2 3p5 1 electron added to the 3p orbital
Cl¯ 1s2 2s2 2p6 3s2 3p6

FIRST ROW TRANSITION METALS

Despite being of lower energy and being filled first, electrons in the 4s orbital
are removed before any electrons in the 3d orbitals.

TITANIUM Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2

Ti+ 1s2 2s2 2p6 3s2 3p6 4s1 3d2
Ti2+ 1s2 2s2 2p6 3s2 3p6 3d2
Ti3+ 1s2 2s2 2p6 3s2 3p6 3d1
Ti4+ 1s2 2s2 2p6 3s2 3p6 62
Dept. of Chemistry, SUST