Contents

6: ATOMIC STRUCTURE AND PERIODICITY ............................................................................................... 2

6.1 ELECTROMAGNETIC RADIATION .................................................................................................... 2
6.1.1 Quanta and Photons - Planck’s Quantum Theory .............................................................. 3
6.1.2 The Photoelectric Effect .......................................................................................................... 4
6.2 THE BOHR MODEL OF THE ATOM ................................................................................................... 4
6.3 THE QUANTUM MECHANICAL MODEL OF THE ATOM .................................................................................. 5
6.3.1 The Dual Nature of the Electron and the de Broglie Relation ................................................... 5
6.3.2 Quantum Mechanics ............................................................................................................... 6
6.3.3 Description of Orbitals by Quantum Numbers ......................................................................... 7
6.4. THE ELECTRONIC STRUCTURE OF ATOMS .................................................................................... 12
6.4.1 Electronic Configuration ........................................................................................................ 12
6.4.2 Electronic Configuration ........................................................................................................ 16
6.4.3 General Rules for Assigning Electrons to Atomic Orbitals ....................................................... 17
6.4.3 Building-up (or Aufbau) Principle and the Periodic Table ....................................................... 18
6.5. PERIODICITY OF THE ELEMENTS .................................................................................................. 21
6.5.1 groups, periods as well as (s, p, d, and f) blocks of the periodic table..................................... 21
6.5.2 Electronic Configurations of Cations and Anions .................................................................... 21
6.6 TRENDS IN THE PERIODIC TABLE (SOME PERIODIC PROPERTIES) .................................................. 22
6.6.1 Atomic Radius ....................................................................................................................... 22
6.6.2 Ionic Radius ........................................................................................................................... 23
6.6.3 Ionization Energy .................................................................................................................. 23
6.6.4 Electron Affinity .................................................................................................................... 23

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6: ATOMIC STRUCTURE AND PERIODICITY
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6.1ELECTROMAGNETIC RADIATION
One of the ways that energy travels through space is by electromagnetic radiation. Figure 6.1
shows the various forms of electromagnetic radiation.
Figure 6.1: Types of Electromagnetic Radiation (wavelengths in metres)

Explanation of electronic structure of elements started with analysis of light emitted by atoms
when they are energized by flames or in electronic discharges. Hence the preview of light waves
that follows below.
A light wave has three main descriptors, namely; intensity or amplitude, wavelength and
frequency. Its speed in terms of frequency and wavelength is given by equation 6.1.
𝑐 = 𝜆𝜈 = 3.00 × 108 𝑚/𝑠 (6.1)
where λ is the wavelength in metres and ν is the frequency in Hertz.

Continuous Spectrum
Visible light passed through a prism divides into its component colours called a continuous
spectrum. This is because all wavelengths of visible light are present in the resulting “rainbow”.

Line Spectra
Light emitted by a discharge tube of a gas like hydrogen or sodium vapor has only a few
coloured lines and is thus called a line spectrum. Since line spectra light is emitted by excited
atoms of an element, it is also referred to as an atomic emission spectrum or emission spectrum
or atomic spectrum. Each element has a unique line spectrum that can be used to identify it.
This fact is the basis of the instrumental analytical technique called Atomic Emission
Spectrometry.
Occurrence of line spectra puzzled physicists for many years. In 1884 Johann Balmer (1825–
1898) found a relatively simple equation shown below for explaining the wavelength of all the
lines in the visible spectrum of hydrogen.

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 1 1 1
𝜆
= 109678 × (22 − 𝑛2 ) cm−1 (6.2)
where λ is the wavelength in cm and n is an integer with values 3, 4, 5, …,∞.
By choosing a particular value of n, the wavelength of a line in the spectrum can be calculated.
So when n=3,
1  1 1 
 109678   2  2  cm 1 =15,233 cm-1or λ=6.565x10-5cm = 656.5 nm.
 2 3 
Similarly, when n=4, 5 and 6, λ is computed to be 486.3, 432.4 and 410.3 nm, respectively. All
these lines are called the Balmer Series.

Hydrogen also emits light in the infrared and ultraviolet regions of the electromagnetic
spectrum. The wavelengths of these series of lines can be fitted to the general equation called
the Rydberg Equation that is shown below
 1 
 109678   2  2  cm 1
1 1
(6.3)
  
 n1 n 2 
where n1 and n2 are integers that may assume values of 1, 2, 3, ⋯, ∞ with the
requirement that n2 is always greater than n1.
Thus, when n1=1, the values of n2 can be 2, 3, 4, ⋯,∞ and the lines in the Lyman series are
obtained. When n1=2 and n2=3, 4, 5, ⋯,∞ we get the Balmer series. These and other series are
summarized in Table 6.1 below.

Table 6.1: Series of lines in the hydrogen spectrum

Series n1 n2 Region of spectrum
Lyman 1 2, 3, 4, ⋯, ∞ Ultraviolet
Balmer 2 3, 4, 5, ⋯, ∞ Visible
Paschen 3 4, 5, 6, ⋯, ∞
Brackett 4 5, 6, 7, ⋯, ∞ infrared
Pfund 5 6, 8, 9, ⋯, ∞

6.1.1 Quanta and Photons - Planck’s Quantum Theory

When solids are heated, they emit electromagnetic radiation over a wide range of wavelengths.
Measurements taken in the latter part of the 19th century showed that the amount of radiation
energy emitted by an object at a certain temperature depends on its wavelength. Attempts to
account for this dependence in terms of wave theory and thermodynamic laws were only partially
successful.

Max Planck (1858 – 1947) solved the problem by departing from the classical physics assumption
that atoms and molecules emit (or absorb) any arbitrary amount of radiant energy. He said that
vibrating atoms and molecules of an object could emit (or absorb) energy only in discrete
quantities that he called quanta. The energy E of a single quantum of energy is given by the
equation

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 E  nh (6.4)

where n=1, 2, 3, ⋯∞ is a quantum number,h is Planck’s constant and ν is the frequency

of radiation.

6.1.2 The Photoelectric Effect

In 1905, Albert Einstein (1879-1955) explained the photoelectric effect (a phenomenon in which
electrons are ejected from the surface of certain metals exposed to light of at least a certain
minimum frequency, called the threshold frequency) using Planck’s quantum theory.
KE = hν – BE (6.5)

where KE is the kinetic energy of the photoelectron, h is the photon energy of the light
exciting the electrons and BE is the binding energy of the photoelectron.

This work corroborated Planck’s quantum theory.

6.2 THE BOHR MODEL OF THE ATOM

In 1913 Neils Bohr (1885-1962) incorporated the ideas of Planck and Einstein into a theory that
enabled him to calculate the energy of the electron in the hydrogen atom.

Bohr postulated that because atoms do not collapse and because light is emitted by an atom
only at certain frequencies, the electron in an atom can possess only certain, restricted quantities
of energy, that is, electron energy in the hydrogen atom is quantized and is given by the equation

1
E n  A  (6.6)
n2

where A is a constant (2.18  10 18 J ) and n is an integer, called a quantum number that
can only have whole number values of 1, 2, 3, ⋯,∞.

Figure 6.2: Bohr model of the Atom

Bohr mathematically derived an equation for the wavelengths of light emitted by hydrogen when
it produces its atomic spectrum. According to Bohr, energy absorption leads to an atom’s

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 excitation from a low energy level like n=1 to a higher level like n=2 and light energy emission
leads to an atom’s de-excitation from higher level like n=2 to a lower level, n=1.

The difference in energy leading to light emission is given by the equation E  E n 2  E n1 which on
substituting in the above equation leads to

 1   1   1 1 
 
E  E n 2  E n1    A 2     A 2  , that is, E  A 2  2  (6.7)
 n2   n1   n1 n 2 

If we substitute the right hand side (RHS) of the equation with E  h into the left hand side
(LHS) of the above equation, we have
 1 1 
h  A 2  2  (6.8)
 n1 n 2 
c hc  1 1 
Putting   into the LHS of the above equation gives  A 2  2  which on dividing with hc
   n1 n 2 
on both sides gives
1 A  1 1 
  (6.9).
 hc  n12 n 22 
This equation is the Rydberg Equation cited earlier as Equation 6.3. Thus, Bohr’s theory firmly
established the concept of atomic energy levels. It was unsuccessful, however, in accounting for
the details of atomic structure and in predicting energies of complex atoms and has since been
replaced by a more successful one.

6.3THE QUANTUM MECHANICAL MODEL OF THE ATOM

Physicists were puzzled by Bohr’s theory. They questioned why energies of the hydrogen electron
are quantized. Or why the electron in a Bohr atom is restricted to orbiting the nucleus at certain
fixed distances.

6.3.1 The Dual Nature of the Electron and the de Broglie Relation
In 1924 Louis de Broglie (1892-1977) provided a solution to this puzzle. de Broglie reasoned that
if light waves can behave like a stream of particles (called photons), then perhaps particles such
as electrons can possess wave properties. According to de Broglie, an electron bound to the
nucleus of atom behaves like a standing wave.

De Broglie argued that if an electron does behave like a standing wave in the hydrogen atom, the
length of the wave must fit the circumference of the orbit exactly. The relation between the
circumference of an allowed orbit (2πr) and the wavelength of the electron is given by
2r  n (6.10)
The circumference of the orbit is equal to an integral number of wavelengths. This is an allowed
wavelength.

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 De Broglie’s reasoning led to the conclusion that waves can behave like particles and particles
can exhibit wave like properties. His argument proceeded as follows.

Einstein had shown that the energy equivalent, E, of a particle of mass is equal to
𝐸 = 𝑚𝑐 2 (6.11)
where c is the speed of light.
A photon whose energy is E could thus be said to have an effective mass equal to m. Max Planck
had shown that the energy of a photon is given by the equation
hc
E  h  (6.12)

Equating the two right hand sides of the above two equations gives
hc
 mc 2 (6.13)

h
This equation when solved for λ gives   . If this equation also applies to particles, such as
mc
electrons, the above equation can be written as
h
 (6.14)
mu
where λ, m and u are the wavelength associated with a moving particle of mass m and
velocity u.
Indeed shortly after de Broglie introduced this equation, Clinton J. Davisson (1881-1958), Lester
H. Germer (1896-1972) and George Paget Thomson (1892-1975) demonstrated the electron’s
wavelike properties by producing a diffraction pattern of an aluminium foil like a diffraction
pattern of x-rays.

6.3.2 Quantum Mechanics

Bohr’s suggestion that the energy of an electron in atom is quantized remains unchallenged. But
his theory did not provide a complete description of electronic behaviour in atoms. For example
(i) Bohr’s approach did not account for emission spectra of atoms containing more than one
electron such as atoms of helium (He) or lithium (Li)
(ii) Bohr’s approach did not explain why extra lines appear in the hydrogen atom’s emission
spectrum when a magnetic field is applied to the atom.
(iii) Another problem arose with the discovery that electrons are wavelike: How can the
“position” of a wave be specified. We cannot define the precise location of a wave
because a wave extends in space.

In describing the problem of trying to locate a subatomic particle that behaves like a wave,
Werner Heisenberg (1901-1976) formulated the Heisenberg Uncertainty Principle which states
that it is impossible to know simultaneously both the momentum p (defined as mass times
velocity) and the position of a particle, 𝑥, with certainty. Stated mathematically,
h
xp  (6.15)
4

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 Where x and  p are the uncertainties in measuring the position and momentum of the
particle, respectively. Making the measurement of the momentum of a particle more precise
(that is,  p making a small quantity) means that the position must become correspondingly less
precise (that is, x will become larger).
Applying the Heisenberg Uncertainty Principle to the hydrogen atom, we see that in reality the
electron does not orbit the nucleus in a well-defined path, as Bohr thought. If it did, we could
determine precisely both the position of the electron (from its location on a particular orbit)
and its momentum (from its kinetic energy) at the same time, a violation of the Uncertainty
Principle.

In 1926, Erwin Schrödinger (1887-1961) using complicated mathematics to investigate standing

waves in the hydrogen atom, began a field of study called Wave or Quantum Mechanics. He
used a complicated mathematical technique to formulate a mathematical equation called a Wave
Equation that describes the behaviour and energies of sub-microscopic particles in general. His
equation is analogous to Newton’s Laws of motion for macroscopic objects. The Schrödinger
Equation requires advanced calculus to solve. It incorporates both particle behaviour, in terms of
mass m, and wave behaviour, in terms of a wave function (usually represented by the symbol psi,
ψ) that describes the shape and energy of an electron wave. Each of different wave is called an
orbital (to distinguish it from Bohr’s orbits). Each orbital in an atom with a characteristic energy is
viewed as describing a region around the nucleus where the electron can be expected to be
found.

6.3.3 Description of Orbitals by Quantum Numbers

The wave functions describing orbitals are characterized by the values of three quantum
numbers. According to Quantum Mechanics, each energy level in an atom is associated with one
or more orbitals. In atoms that contain more than one electron, the distribution of electrons
about the nucleus is determined by the number and kind of orbitals occupied. Therefore, in order
to investigate the way electrons are arranged in space we must first examine the energy levels in
the atom. This is best accomplished through a discussion of the quantum numbers.
6.3.3.1 The Principal Quantum Number, n
Energy levels in an atom are arranged roughly into main levels or shells determined by the
principal quantum numbers, n. The larger n is, the greater the average energy of the levels
belonging to the shell and the further is the electron from the nucleus. As in the Bohr Theory, n
may have integral values ranging from one to infinity, that is, 1, 2, 3, ∙∙∙,∞. Letters are also
associated with these shells as shown below
Principal Quantum Number 1 2 3 4 . . .
Letter Designation K L M N . . .
For example, sometimes the shell with n=1 is referred to as the K shell.

6.3.3.2 The Azimuthal or Angular Momentum Quantum Number, l

Wave Mechanics predicts that each main shell is composed of one or more subshells or
sublevels, each of which is specified by a secondary quantum number, l, called the azimuthal

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 (or angular momentum) quantum number. This quantum number determines the shape and to
some extent the energy of an orbital. For any given shell, l, may have values of 0, 1, 2, 3, …, n-1
for that shell. Thus, when n=1, the value of l=0. Therefore the K shell has one orbital. When
n=2, two values of l occur, namely, l=0 and l=1; hence the L shell is composed of 2 subshells.
The values of l that occur for each value of n are summarized in Table 6.2 below.
Table 6.2: Principal quantum numbers and azimuthal quantum numbers
n l
1 0
2 0,1
3 0,1,2
4 0, 1, 2, 3
. .
. .
. .
n 0, 1, 2, 3, . . ., n-1

The number of subshells in any given shell is simply equal to the value of n for that shell. For
purposes of discussing the distribution of electrons in an atom, it is common practice to
associate letters with various values of l
Value of l 0 1 2 3 4 5 6 . . .
Subshell classification s p d f g h i . . .

Sharp principal diffuse fundamental

In our study of periodic table elements, we will only be interested in s, p, d and f subshells
because they are the ones populated by electrons in the atoms in their ground state (or state
of lowest energy).
To specify a subshell within a given shell, we write the value of n for the shell followed by the
letter designation of the subshell. For example, the s subshell of the second shell (n=2, l=0) is
called the 2s subshell. Similarly, the p subshell of the second shell (n=2, l=1) would be the 2p
subshell.

6.3.3.3 The Magnetic Quantum Number, ml

Each subshell is composed of one or more orbitals. An orbital in a particular subshell is
distinguished by its value of ml, which serves to determine its orientation in space relative to
other orbitals. The magnetic quantum number derives its name from the fact that it can be
used to explain the appearance of additional lines in atomic spectra produced when atoms
emit light while in a magnetic field. It has integer values that range between –l and +l. When
l=0, there is only one value of ml=0; therefore an s subshell consists of only one orbital (we call
it an s orbital). A p subshell (l=1) consists of three orbitals corresponding to ml equal to −1, 0,
and +1. Similarly, d subshell (l=2) consists of five orbitals and the f subshell (l=3) has seven
orbitals. This is summarized in Table 6.3 below where the simple progression of orbitals is to be

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 noted as 1, 3, 5, 7 and so on. The formula for the total number of orbitals in a given subshell is
2l+1.
Table 6.3: Summary of Quantum Numbers
Principal Quantum Azimuthal Quantum Subshell Magnetic Quantum No. of orbitals in
No., n (shell) No., l (Subshell) Designation No., ml (orbital) Subshell (2l+1)
1 0 1s 0 1
0 2s 0 1
2
1 2p -1,0,1 3
0 3s 0 1
3 1 3p -1,0,1 3
2 3d -2,-1,0,1,2 5
0 4s 0 1
1 4p -1,0,1 3
4
2 4d -2,-1,0,1,2 5
3 4f -3,-2,-1,0,1,2,3 7

6.3.3.4 Energy Levels of Atomic Orbitals – Madelung’s n+l Rule

Figure 6.3: Energy of orbitals of a hydrogen atom

4s ___ 4p ___ ___ ___ 4d ___ ___ ___ ___ ___ 4f ___ ___ ___ ___ ___ ___ ___
Energy
3s ___ 3p ___ ___ ___ 3d ___ ___ ___ ___ ___

2s ___ 2p ___ ___ ___

1s ___

Please note from Figures 6.3 and 6.4: Orbitals with the same energy are said to be degenerate
1. All orbitals in shells with more than one orbital in a hydrogenic atom are degenerate, that
is, they have the same energy.
2. In a polyelectronic atom, only orbitals of a subshell with more than one orbital are
degenerate.

The order in which these orbitals are filled in polyelectronic atoms is given by the n+l Rule (also
known as the Madelung rule (after Erwin Madelung, 1881-1972), or the Janet rule or
the Klechkowsky rule, (after Charles Janet, 1849-1932 or Vsevolod Klechkovsky, 1900-1972 in
some, mostly French and Russian-speaking, countries) or the diagonal rule. Orbitals with a
lower n+l value are filled before those with higher n+l values. In this context, n represents
the principal quantum number and l the azimuthal quantum number; the values l = 0, 1, 2, 3
correspond to the s, p, d, and f labels, respectively. The Madelung rule states that atomic
orbitals are filled in order of increasing n+l quantum numbers. A refinement of this rule is that
when two values of n+l are equal, the orbital with a lower principal quantum number, that is

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lower a n value, will be filled first (e.g. 3d < 4p). Thus the order is
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d<7p as shown by Figure 6.5.

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 Figure6.4: Approximate energy level diagram for atomic orbitals of multielectron atoms.

7s ___ 5f ___ ___ ___ ___ ___ ___ ___ n=7

6p ___ ___ ___
5d ___ ___ ___ ___ ___ 4f ___ ___ ___ ___ ___ ___ ___n=6
6s ___

5p ___ ___ ___

4d ___ ___ ___ ___ ___ n=5

5s ___

4p ___ ___ ___

n=4
3d ___ ___ ___ ___ ___
4s ___
Energy

3p ___ ___ ___ n=3

3s ___

2p ___ ___ ___

n=2

2s ___

1s ___ n=1

The energies of the shells, subshells and orbitals in multielectron atoms are perhaps best
illustrated by Figures 6.4 and 6.5.

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 Figure 6.5: Order of atomic subshells filling in many-electron atoms.

https://en.wikipedia.org/wiki/File:Aufbau_Principle.png
The states crossed by same red arrow have same n + l value. The direction of the red arrow
indicates the order of state filling while the direction of the blue line shows the basis of the name
“diagonal rule”.

6.4. THE ELECTRONIC STRUCTURE OF ATOMS

6.4.1 Electronic Configuration
After we learn about the fourth quantum number (m s), we will start learning about electronic
configuration of atoms by using Madelung’s n+l rule, the Pauli Exclusion Principle, shapes and
orientations of atomic orbitals to determine sets of four quantum numbers for electrons of the
ground states of the first 10 elements.
6.4.1.1Electron Spin Quantum Number (ms) and Pauli Exclusion Principle
In addition to the 3 quantum numbers n, land ml which come from solving of the wave equation,
there is a fourth one called the spin quantum number ms.This quantum number arises because
the electron behaves as if it were spinning. Since the electron can only spin in either of two
directions, ms may have only two values. These are +½ and -½.

We find, therefore, that each electron in an atom can be assigned a set of values for its four
quantum numbers n, l, ml and ms which determine the orbital in which the electron will be found
and the direction in which the electron will be spinning.

6.4.1.2Pauli Exclusion Principle

There is restriction however, on the values that these quantum numbers can have. This is
expressed as the Pauli Exclusion Principle which states that no two electrons in any atom may
have all four quantum numbers the same. This limits the number of electrons in any given orbital
to two and it also requires that the spins of these two electrons be in opposite directions.

Because the Pauli Exclusion Principle leads to a restriction of a maximum of two electrons in any
orbital, the maximum number of electrons that can be accommodated in s, p, d and f subshells is
summarized in Table 6.4 below.

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 Table 6.4: Maximum electrons per subshell of an atom
Subshell Number of Orbitals Subshell Maximum Number of Electrons = 2(2l+1)
s 1 2
p 3 6
d 5 10
f 7 14
Thus the maximum number of electrons in any shell is equal to 2n2. For example, K shell (n=1) has
two (2  12=2) electrons and the L shell (n=2) holds a maximum of eight electrons (2  22=2  4=8).

The spin of an electron is also responsible for most of the magnetic properties in atoms and
molecules.

Diamagnetic materials experience no attraction to a magnet. In these substances the number of

electrons with upward spin is the same as those with downward spin so that magnetic effects of
electrons with upward spin cancel out the magnetic effects of electrons with downward spin.

Paramagnetic materials are weakly attracted to a magnetic field. In these materials there are
more electrons of one spin than the other (as in the case of an atom or a molecule with an odd
number of electrons) so that total cancellation of magnetic effects does not occur. The extra
electrons of one spin cause the atom or molecule, as whole, to behave as if it were itself a tiny
magnet.

Ferromagnetic materials like iron owe their very strong magnetic behaviour to interactions
among paramagnetic atoms in the solid state. Ferromagnetism is about 106 times stronger than
paramagnetism.

6.4.1.3Atomic Orbitals
We have seen the relation between quantum numbers and atomic orbitals. When l=0, there is
only one ml value so that the number of orbitals given by the equation (2l+1) is one, and we have
an s orbital. When l=1 and (2l+1)=3 we have three values of ml or three p orbitals. When l=2 and
(2l+1)=5 there are 5 orbitals of ml values that are five d orbitals. Below we consider the s, p and d
orbitals separately.
s Orbital
The shape of an s of orbital is that of a sphere of a boundary surface diagram that encloses
about 90% of the total electron density.
Energy and size of s orbitals increases with n, that is, 1s<2s<3s … in both energy and size as
shown in Figure 6.6 below.
Figure 6.6: Spherical Shape of the First Three sOrbitals and Their Relative Sizes

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p Orbitals
These start with principal quantum number n=2 when l=1 and ml has values -1,0, and 1 which
result in three p orbitals designated as 2px, 2py and 2pz. The letter subscripts indicate the axes
along which the orbitals are oriented. Figure 6.7 shows these orbitals. It is apparent from the
figure that p orbitals only differ in orientation. Their boundary surface diagrams have two lobes
on opposite sides of the nucleus of the atom. Like s orbitals, p orbitals increase in size from 2p
to 3p to 4p orbitals and so on.

Figure 6.7: p Orbitals Lying Along Three Perpendicular Axes

d Orbitals and other Higher Orbitals

When n≥3 and l=2, there are five (2l+1) values of ml(that is, -2, -1, 0, 1, and 2) which
correspond with five d orbitals. Thus the first d orbitals occur in the level n=3. These d orbitals
have two different fundamental shapes. Four of the orbitals ( d xy , d yz , d xz , and d x 2  y 2 ) have

four lobes centred in the plane indicated in the name of the orbital. Note that dxy and d x 2  y 2 are

both centred in the xy plane, however, the lobes of the d x 2  y 2 orbital lie along the x and y axes
while the lobes of the dxy orbital lie between the axes at 45. The dyz and dxz are similarly lie at
45 degrees of the name axes. The fifth orbital, d z 2 , has two lobes along the z axis plus a donut
of electron density centred in the xy plane. The d orbitals for levels n>3 look like the 3d orbitals
but have larger lobes and are further from the nucleus of the atom. All these orbitals are
shown in Figure 6.8 below.

Figure 6.8: The Five d Atomic Orbitals of Elements

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The f orbitals have more complicated shapes than d orbitals. The first f orbitals occur in the
level n=4 when l=3 so that (2l+1)=7 and there 7 f orbitals. The f orbitals are not involved in
bonding of compounds considered in freshman chemistry and are simply covered here for
completeness.

Like d orbitals, shapes of f orbitals consist of two groups. The first group of three orbitals have a
pair of lobes lying along the principle axes on opposite sides of the nucleus of the atom. Each
lobe’s shape is somewhat like a medicine dropper tit. They are labelled f z 3  3 zr 2 , f y 3  3 yr 2 , and
5 5

f x 3  3 xr 2 . Each of the remaining four orbitals consists of eight lobes that are arranged in four
5

pairs. Each pair of lobes lies on diametrically opposite sides of the atom’s nucleus and are
labelled f xyz , f y ( x 2  y 2 ) , f x ( z 2  y 2 ) , and f z ( x 2  y 2 ) . Diagrams of these seven f orbitals are shown
in Figure 6.9. Table 6.5 summarizes information outlined above on s, p, d and f orbitals.

Figure 6.9: The Seven f Atomic Orbitals of Elements

Table 6.5: Table of Relation between Quantum Numbers and Atomic Orbitals.
n l No. of orbitals (2l+1) Atomic orbital Designation Comment
1 0 1 1s s subshell K shell with one orbital
0 1 2s s subshell 4 orbitals in 2 subshells make
2
1 3 2px,2py,2pz p subshell the L shell
3s s subshell
0 1
3px,3py,3pz p subshell 9 orbitals in 3 subshells make
3 1 3
3dxy,3dyz,3dxz, 3d x 2  y 2 , 3d z 2 d subshell the M shell
2 5
. . . . . .
. . . . . .
. . . . . .

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6.4.2Electronic Configuration

6.4.2.1 Labelling Electrons

The four quantum numbers allow us to label electrons in an atom. The simplified labelling
notation consists of the four quantum numbers in brackets, that is, (n, l, ml, ms). For example,
an electron with the following quantum numbers n=2, l=0, ml=0, ms =+½ or ms =-½ can be
labelled a (2, 0, 0, -½) or (2, 0, 0, +½). It is to be noted that m s has no effect on energy, shape or
orientation but affects the way electrons are arranged in an orbital.

Example: Write the possible sets of four quantum numbers of a 5p orbital electron.

Answer: We need to write all (n, l, ml, ms) possible values. We know that n=5 and l=1 but ml
and ms are not specified. Possible values are tabulated below.

n l ml ms
-1 +½
-1 -½
0 +½
5 1
0 -½
1 +½
1 -½
Thus, the possible sets of 4quantum numbers for an electron in a 5p orbital are (5, 1, -1, +½),
(5, 1, -1, -½), (5, 1, 0, +½), (5, 1, 0, -½), (5, 1, 1, +½), (5, 1, 1, -½).

6.4.2.2 Electron Configuration of an Atom and Hund’s Rule

This is how the electrons are distributed among the various atomic orbitals. We write this for
the ground state of an atom. Below, we give electronic configurations for the first two periods
of the periodic table.

Element Atomic Number Configuration spin Orbital Diagram

Hydrogen Z=1 1s1 H 1s1

Principal quantum numberNumber of electrons in the orbital or subshell

Angular momentum quantum number l (letter designation)
Helium Z=2 1s2 He 1s2

NB: When using the spin diagrams we have 3 possibilities. (a) (b) and (c)

The Pauli Exclusion Principle which states that no two electrons in an atom can have the same
four quantum numbersprecludesspin diagrams (b) and (c).

Element Atomic Number Configuration Spin Orbital Diagram

Li 3 1s22s1 or
[He]2s1 1s22s1
Be 4 1s22s2or

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 [He]2s2 1s22s2
B 5 1 22s22p1
[He]2s22p1 1s2 2s22p1

The unpaired electron can be in the 2px, 2py or 2pz orbital. Choice is arbitrary because thelevels
are degenerate.
C 6 1s22s22p2
[He]2s22p2 1s2 2s2 2p2
NB: The two electrons in the p shell can be distributed among three p orbitals without violating
the Pauli Exclusion Principle as follows
(a) (b) (c)

2px 2py2pz 2px 2py 2pz 2px 2py 2pz

But the arrangement of greatest stability, that is, the acceptable orbital diagram, (a), is
provided by Hund’s rule which states that the most stable arrangement of electrons in a shell is
the one with the greatest number of parallel electrons. The fact that (a) is paramagnetic is in
accord with Hund’s rule.
N Z=7 1s22s22p3
[He]2s22p3 1s2 2s2 2p3
Hund’s rule dictates that all three 2p electrons have parallel spin. N is paramagnetic, containing
three unpaired electrons.
O Z=8 1s22s22p4
[He]2s22p4 1s2 2s2 2p4
O is paramagnetic, because it contains two unpaired electrons.
F Z=9 1s22s22p5
[He]2s22p5 1s2 2s2 2p5
F is paramagnetic.
Ne 2=10 1s22s22p6
[He]2s22p6 1s2 2s2 2p6
Ne is diamagnetic. All orbitals with n=1 and n=2 are completely filled.

6.4.3General Rules for Assigning Electrons to Atomic Orbitals

(i) Each shell (or principal level) of quantum number n contains n subshells (or values of l), for
example, if n=2, there are 2 subshells, namely, that of l=0 and l=1.
(ii) Each subshell of quantum number l contains 2l+1 orbitals. For example, if l=1, there are
three p orbitals (2×1+1=3) whose ml values are −1, 0, and 1.
(iii) (Pauli Exclusion Principle:) No more than two electrons can be placed in each orbital.
Therefore, the maximum number of electrons is simply twice the number of orbitals that are
employed.
(iv) A quick way to determine the maximum number of electrons that an atom can have in
principal level (or shell) n is to use the formula 2n2 since the number of orbitals in principal
level is n2.
Example: What is the maximum number of electrons that can be present in the principal level
for which n=4?
Answer: The two ways of answering this question are

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 (i) When n=4, then l=0, 1, 2 and 3. The number of orbitals for each subshell is shown in the
table below.
l (subshell) 0 1 2 3 Total orbitals
(2l+1) (Number of orbitals) 1 3 5 7 2l  1  16

The total number of orbitals, as shown above, is 16. Since each orbital can accommodate
two electrons (Pauli Exclusion Principle), the maximum number of electrons that can
reside in the orbitals is 2×16=32.
(ii) Using the formula for maximum number of electrons in a shell n given as 2n2.Since we
have n=4, then the maximum electrons are 2(42)=32.

6.4.3Building-up (or Aufbau) Principle and the Periodic Table

In outlining the electronic configurations of the first two periods, we started to use the quantum
mechanical model of the atom to show how the electron arrangements in hydrogen like atomic
orbitals of various atoms account for organization of the periodic table. The main assumption
here is that all atoms have the same type of orbitals as described for the hydrogen atom. As
protons are added one by one to the nucleus to build up the elements, electrons are similarly
added to these hydrogen like orbitals. This statement is called the Aufbau Principle.

Considering where we left off in looking at electronic configuration of atoms, we consider

sodium. Sodium’s first 10 electrons occupy the 1s, 2s and 2p orbitals and the eleventh electron
must occupy the first orbital with n=3, that is, the 3s orbital so that sodium’s configuration is
1s22s22p63s1. To avoid writing inner-level or core electrons, this configuration can be abbreviated
as [Ne]3s1 where [Ne] represents the neon electron configuration, 1s22s22p6.

Similarly, magnesium’s electron configuration is 1s22s22p63s2 or [Ne]3s2.

The next six elements, aluminium through argon have configuration obtained by filling 3p orbitals
one electron at a time. The figure below summarizes the electron configuration of the first 18
elements by giving the number of electrons in the type of outer orbital occupied last.

H He
1s1 1s2
Li Be B C N O F Ne
2s1 2s2 2p1 2p2 2p3 2p4 2p5 2p6
Na Mg Al Si P S Cl Ar
3s1 3s2 3p1 3p2 3p3 3p4 3p5 3p6

At this point it is useful to introduce the concept of valence electrons, that is, the electrons in the
outermost principal quantum level (or shell) of the atom. For the N atom, valence electrons are
the 2s and 2p electrons. For the sodium atom, valence electron is the electron in the 3s orbital,
etc. The valence electrons are the most important electrons to chemists because they are involved
in bonding. The inner electrons are known as core electrons.

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It should be noted in the previous table that a very important pattern is developing, namely;
elements in the same group (vertical column of the periodic table) have the same valence electron
configuration. Recall that Mendeleev originally placed the elements in groups based on
similarities in chemical properties. Now we understand the reason behind these groupings.
Elements with the same valence electron configuration show similar chemical behaviour.

The element after argon is followed by potassium. Since the 3p orbitals are fully occupied in Ar,
we might expect the next electron to go into a 3d orbital (recall that for n=3 the orbitals are 3s,
3p and 3d). However the chemistry of potassium is clearly very similar to lithium and sodium,
indicating that the last electron in potassium occupies the 4s orbital instead of the 3d orbitals, a
conclusion confirmed by many types of experiments and Madelung’s rule. The electron
configuration potassium (K) is 1s22s22p63s23p64s1 or [Ar]4s1. The next element is calcium with an
electron configuration of [Ar]4s2.

The next element, scandium, begins a series of 10 elements (scandium through zinc) called the
transition metals, whose configurations are obtained by adding electrons to the five 3d orbitals.
In this series, additional electrons are placed in the 3d orbitals according to Hund’s rule.
However, there are two irregularities. The electron configuration of Group VI B elements which is
[Noble Gas](n+1)s1nd5 instead of [Noble Gas](n+1)s2nd4. For example, the first Group VI B
element’s, chromium (Z=24), electronic configuration is [Ar]4s13d5 not [Ar]4s23d4. A similar break
in the pattern is observed for Group I B elements which is [Noble Gas](n+1)s1nd10 instead of
[Noble Gas](n+1)s2nd9. For example, the first Group I B element’s, copper (Z=29), electron
configuration is [Ar]4s13d10 rather than [Ar]4s23d9. The reason for these irregularities is that a
slightly greater stability is associated with half-filled (3d5) and completely filled (3d10) subshells.

Cr: [Ar]
4s1 3d5
Cu: [Ar]
4s1 3d10
For elements Zn (Z=30) through Kr (Z=36), the 4s 4p subshells fill in a straight forward manner.

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
4s1 4s2 3d1 3d2 3d3 4s13d5 3d5 3d6 3d7 3d8 4s13d10 3d10 4p1 4p2 4p3 4p4 4p5 4p6

Irregularities

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 With rubidium (Z=37), electrons begin to enter the n=5 energy level. The electron configuration
in the second transition metal series (yttrium, Z=39 to silver, z=47) are also irregular, but we
leave out the details here.

The sixth period begins with cesium (Z=55) and barium (Z=56) whose electron configurations are
[Xe]6s1 and [Xe]6s2, respectively. Next we come to lanthanum (Z=57) for which we would expect
the filling of 4f orbitals. In reality, the energies of the 5d and 4f orbitals are very close; in fact for
lanthanum, the 4f energy level is slightly higher in energy than the 5d level, thus lanthanum
electron configuration is [Xe]6s25d1 not [Xe]6s24f1.

After lanthanum are the 14 elements known as the lanthanides or rare earth elements (cerium,
Z=58 to lutetium, Z=71). The rare earths have an incompletely filled 4f subshell or readily give rise
to cations that have incompletely filled 4f subshells.

The seventh period begins with francium and radium whose electronic configurations are [Rn]7s1
and [Rn]7s2. Next is actinium (Z=89) with an electronic configuration similar to lanthanum, that is,
[Rn]7s26d1. Thereafter the second row of the inner transition metals called actinides starts at
thorium (Z=90). Most of these elements are not found in nature but have been synthesized.

Figure 6.10: Different blocks (s, p, d and f) of the periodic table of elements

Group
IA IIA IIIA IVA VA VIA VIIA VIIIA
1s 1 2 3 4 5 6 7 8 9 10 1s
2 s VIIB 2 p
3 s IIIB IVB VB VIB VIIB IB IIB 3 p
Period

4 s 3 d 4 p
5 s 4 d 5 p
6 s La 5 d 6 p
7 s Ac 6 d

1 2 3 4 5 6 7 8 9 10 11 12 13 14
4 f Lanthanides
5 f Actinides

The entire periodic table is represented in the previous table in terms of which orbitals are filled
(i) The (n+1)s orbitals always fill before nd orbitals in accordance to Madelung’s rule.
(ii) After lanthanum, [Xe]6s25d1, 14 elements called lanthanides have their 4f orbitals filled.
(iii) After actinium, [Rn]7s26d1, 14 elements called actinides have their 5f orbitals filled.
(iv) The group labels IA, IIA, IIIA, IVA, VA, VIA, VIIA and VIIIA are called main-group or
representative elements. It is to be noted that every member of each given group has
the same number of valence electrons.

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6.5. PERIODICITY OF THE ELEMENTS
6.5.1 groups, periods as well as (s, p, d, and f) blocks of the periodic table
If one considers the elements in the periodic table from the point of view of their outermost
ground-state electron configurations starting with hydrogen, it is seen that subshells are filled in
the order shown in Figure 4. According to the type of subshell being filled, the elements can be
divided in the following categories
(i) representative or main group elements,
(ii) noble gases,
(iii) transition elements (or metals), and
(iv) inner transition elements (or metals).

Using the classical numbering of groups, the representative elements are in groups IA to VIIIA. The
noble gases (that is, Group VIIIA) have completely filled s and/or p subshells of the highest principal
quantum number.
The transition metals are elements in groups IB to VIIIB. They have incompletely filled d subshells or
readily produce cations with incompletely filled d subshells. These metals are sometimes referred
to as d-block transition elements.
The inner transition metals (that is, lanthanides and actinides) are sometimes called f-block
transition elements because they have incompletely filled f subshells.
A clear pattern emerges when examining electron configurations of elements of a particular group.
The pattern is that of outer elements of an atom, which are the ones involved in chemical bonding
and are often called valence electrons. The summary for the main-group elements is shown in the
table below where valence electrons are those at the highest principal energy level n.

Element Group Valence electron configuration

IA ns1
IIA ns2
IIIA np1
IVA np2
VA np3
VIA np4
VIIA np5
VIIIA or 0 1s2 for helium and ns2np6 for the rest

6.5.2Electronic Configurations of Cations and Anions

Many ionic compounds are made up of monoatomic anions and cations. Once we know the
number of electrons for the ion, writing the electron configuration of an ionic species uses
Madelung’s rule, the Pauli Exclusion Principle and Hund’s rule just like we do in the case of
writing the electronic configuration of a neutral atom.

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6.5.2.1 Ions Derived from Representative Elements
Ions formed from neutral atoms of most representative elements have a noble-gas outer
electron configuration of ns2np6. Thus, in forming cations, one or more electrons are removed
from the highest occupied nth shell as shown in the table below.

Element Element electron configuration Cation Cation electron configuration

Na [Ne]3s1 Na+ [Ne] or 1s22s22p6
Ca [Ar]4s2 Ca2+ [Ar] or 1s22s22p63s23p6
Al [Ne]3s23p1 Al3+ [Ne]

It is to be noted that each ion has a stable noble gas configuration.

In forming anions, one or more electrons are added to the highest filled nth shell as shown in
the table below.

Element Element electron configuration Cation Cation electron configuration

H 1s1 H− [He] or 1s2
F 1s22s22p5 or [He]2s22p5 F− [Ne] or 1s22s22p6
O 1s22s22p4 or [He]2s22p4 O2− [Ne]
N 1s22s22p3 or [He]2s22p3 N3− [Ne]

All of these anions also have stable noble gas configuration. F − , Na+ and Ne (as well
asMg 2+ ,Al3+ ,O2− and N3− ) have the same electronic configuration. They are said to be
isoelectronic because they have the same ground-state electron configuration.

6.6TRENDS IN THE PERIODIC TABLE (SOME PERIODIC PROPERTIES)

The electron configurations of atoms display a periodic variation with increasing atomic number.
As a result, the elements show periodic variations of physical and chemical behaviour. The
periodic law states that when elements are arranged in increasing order of atomic number,
their physical and chemical properties vary periodically. In the sections below, we look at four
physical properties of an atom: atomic radius, ionization energy, electronegativity and electron
affinity. These quantities, especially the latter three, are important in discussions of chemical
bonding.

6.6.1 Atomic Radius

Atomic radius is defined as one-half the distance between the two nuclei in two adjacent
atoms.
In a given period of main-group elements (that is, for a given principal quantum number), the
effective nuclear charge increases across the period, therefore, the atomic radius decreases
across the period.
In a given group of main-group elements, the atomic radius increases down the group, that is,
with increasing atomic number. This is because orbital size increases with increasing principal
quantum number n.

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6.6.2 Ionic Radius
Ionic radius is the radius of a cation or anion.
When a neutral atom is converted to an ion, we expect a change in size. If an atom forms an
anion, its size (or radius) increases because of increased repulsion among electrons. On the
other hand, removing an electron or electrons from an atom, the resulting cation is smaller
because remaining electrons, being fewer, are bound more tightly.

6.6.3 Ionization Energy

Ionization energy is the minimum energy (in kJ/mol) required to remove an electron from a
gaseous atom in its ground state. Its magnitude measures how tightly an electron is held in the
atom.
Ionization energy ⇒ Energy  X (g )  X (g )  e  ejected electron
gaseous atom of element X gaseous ion of element X

The higher the ionization energy, the more difficult it is to remove the electron.
For many electron atoms,
energy to remove the first electron is called 1stionization energy (I1),
energy to remove the second electron is called 2nd ionization energy (I2),
etc.
When an electron is removed from a neutral atom, the repulsion among remaining electrons
decreases. Since nuclear charge is constant, more energy is needed to remove another electron
from a positively charged ion. Thus I1< I2< I3< …

Generally, metals have lower ionization energies than non-metals, that is, in a period, the
general trend is that ionization energy increases across the period. Ionization energy of
metalloids is between that of metals and non-metals.

There are parallel trends between atomic radii and ionic radii in a group, that is, ionic radii, like
atomic radii, increase down a group.

When focusing on isoelectronic cations in a particular period, radii of tripositive ions (ions that
have three positive charges) are smaller than dipositive ions (ions that bear two positive
charges) which in turn is smaller than unipositive ions, for example, rAl3  rMg 2  rNa  .
When considering isoelectronic anions, ionic radius increases from ions with uninegative
charge (-) to those with dinegative charge (2-) and so on; for example rF− < rO2− < rN3− .

6.6.4 Electron Affinity

This is a property that measures the ability of an atom to accept one or more electrons.
Electron affinity is defined as the negative of the energy change that occurs when an electron is
accepted by an atom in the gaseous state to form an anion.
X (g )  e   X (g )

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If we consider the process in which a gaseous fluorine atom accepts an electron, we have
F(g )  e   F(g ) H  328 kJ / mol
The electron affinity of fluorine is therefore assigned a value of +328 kJ/mol. The more +ve is
the electron affinity of an element the greater is the affinity of an atom of the element to
accept an electron.
Another way of looking at electron affinity is to think of it as the energy that must be supplied
to remove an electron from an anion. For fluorine, we have
F(g )  F(g )  e  H  328 kJ / mol
For main group elements, the trend is that electron affinity increases from left to right, that is,
electron affinity of metals is lower than that of non-metals. The halogens have the highest
electrons affinity values. This is so because when halogens get an electron the resulting
configuration is very stable.

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