THE PERIODIC TABLE AND

ATOMIC STRUCTURE

Dr. Mar Lar Than

Professor & Head
Department of Engineering Chemistry
 The Electromagnetic Spectrum

Electromagnetic radiation – the transmission of energy

through oscillating electric and magnetic fields at the speed
of light.
Characteristics of a wave –
1. wavelength – the distance between corresponding points
on adjacent waves. (λ , unit = m, nm)

2. frequency – the number of complete cycles of the wave

passing a given point per second (ʋ, 1/s or Hz)

3. amplitude – the size or height of the wave.

4. velocity – speed of light - constant

( c = 2.998 x 𝟏𝟎𝟖 m𝐬 −𝟏 )
 Light has a fixed speed, its frequency and wavelength are always inversely
related.
- amplitude – independent of frequency
c=λʋ
- higher the frequency, shorter the wavelength
- larger the amplitude, brighter the light

- Refraction – the bending of a wave when it passes from one medium to

another of different refractive index.
Example 6.1 – Carbon can be detected in an X-ray fluorescence experiment by
monitoring the emission at a wavelength of 4.47 nm. What is the frequency of this
light?
λ = 4.47 nm = 4.47 x 𝟏𝟎−𝟗 m
c=λʋ
2.998 x 𝟏𝟎𝟖 m𝐬−𝟏
ʋ = c/ λ = = 6.71x 𝟏𝟎𝟏𝟔 𝐬 −𝟏
4.47 x 𝟏𝟎−𝟗 m
Photoelectric Effect -
in which light strikes a piece of metal and causes electrons to
be ejected. 1 Photons of su cient energy strike a metal surface 2 The ejected electrons are collected
and electrons are ejected. by the anode.

Electron
Electron (–)

Light Photo cathode (–)

Anode (+)

Meter
(current)

3 The movement of the photoelectrons causes a current

to flow, and allows the light intensity to be monitored.
 # e–
y > y0

(a) y0 y (b) I

KE
y > y0

 The graphs sketched here show the most important observations from experiments
on the photoelectric effect.
Below some threshold frequency (ν0), no photoelectrons are emitted. For frequencies greater than ν0, the
number of electrons emitted is independent of frequency (graph a) but increases with increasing light
intensity (graph b). The kinetic energy of the emitted electrons, on the other hand, increases linearly with
frequency (graph c) but is independent of intensity (graph d).
 Wave-particle duality
– in some situations, light is best described as a wave whereas in
other cases, a particle description works better.
- Neither the wave model nor the particle model provides an
accurate description of all the properties of light.
- Albert Einstein proposed – the light could be described as a
collection of packets of energy, photons.
hc
E=hʋ = ( h = 6.626 x 𝟏𝟎−𝟑𝟒 J s = Plank’s constant)
λ
- lower the frequency, longer the wavelength, lower the energy
ʋ↓ λ↑ E↓
 Example 6.2
Chromium can be detected in atomic absorption spectroscopy by
monitoring the absorbance of UV light at a wavelength of 357.8 nm.
What is the energy of a photon of this light?

λ = 357.8 nm = 357.8 x 𝟏𝟎−𝟗 m

hc 6.626 x 𝟏𝟎−𝟑𝟒 J s 𝒙 2.998 x 𝟏𝟎𝟖 m𝐬−𝟏
E= = = 5.552 x 𝟏𝟎−𝟏𝟗
J
λ 357.8 x 𝟏𝟎−𝟗 m

Question - The specifications for a handheld XRF analyzer indicate that the X-ray
source emits photons with an energy of 8048.0 eV.
What is the wavelength of these X-rays?
(electron-volt; 1 eV = 1.6022 × 𝟏𝟎−𝟏𝟗 J)
Electron Binding energy (ionization energy) – the amount of energy
 required to remove an electron from an atom, molecule or ion.

 Below the threshold frequency, a photon does not have enough energy to
overcome the binding energy and eject the electron.

 Why does the electron kinetic energy depend on the frequency of the light?
 electron binding energy of a particular metal, is fixed.

 Ephoton = Binding energy + Kinetic energy (electron in atom)

 Example 6.3
 In a photoelectric effect experiment, ultraviolet light with a wavelength of
 337 nm was directed at the surface of a piece of potassium metal. The kinetic
 energy of the ejected electrons was measured as 2.30 × 10-19 J. What is the
 electron binding energy for potassium?
 λ = 337 nm = 337 x 𝟏𝟎−𝟗 m
hc 6.626 x 𝟏𝟎−𝟑𝟒 J s 𝒙 2.998 x 𝟏𝟎𝟖 m𝐬−𝟏
 E= = = 5.89 x 𝟏𝟎 −𝟏𝟗
J
λ 337 x 𝟏𝟎−𝟗 m

 Ephoton = Binding energy + Kinetic energy

 Binding energy = Ephoton − Kinetic energy
 = 5.89 x 𝟏𝟎−𝟏𝟗 J − 2.30 x 𝟏𝟎−𝟏𝟗 J
 = 3.59 x 𝟏𝟎−𝟏𝟗 J

 The electron binding energy for chromium metal is7.21 × 10-19 J.

Find the maximum kinetic energy at which electrons can be ejected from chromium in a
photoelectric effect experiment using light at 266 nm.
Atomic Spectra (atomic spectrum)
- the particular pattern of wavelengths absorbed and emitted by
any element.

Gas discharge tube containing

hydrogen

Prism

When an electric discharge is applied to a sample of hydrogen gas, H2 molecules

dissociate into atoms, and those atoms then emit light. That light passes through a set of
slits to create a narrow beam of light, which then passes through a prism. The prism
separates the light into its constituent colors and shows that only a few discrete
wavelengths are emitted.
Example 6.4
 The first four energy levels for the hydrogen atom are shown in the diagram
below. The lowest energy state is labeled E1, and the higher states are labeled E2, E3,
and E4, respectively. When a hydrogen atom undergoes a transition from E3 to E1, it
emits a photon with λ = 102.6 nm. Similarly, if the atom undergoes a transition from
E3 to E2,it emits a photon with λ = 656.3 nm. Find the wavelength of light emitted by
an atom making a transition from E2 to E1.

𝐸3
λ = 656.3 nm
E 𝐸2

λ = 102.6 nm

𝐸1
 𝐄𝟑→𝟏 transition, λ = 102.6 nm = 102.6 x 𝟏𝟎−𝟗 m
hc 6.626 x 𝟏𝟎−𝟑𝟒 J s 𝒙 2.998 x 𝟏𝟎𝟖 m𝐬−𝟏
 𝐄𝟑→𝟏 = = = 1.936 x 𝟏𝟎 −𝟏𝟖 J
λ 102.6 x 𝟏𝟎−𝟗 m

 𝐄𝟑→𝟐 transition, λ = 656.3 nm = 656.3 x 𝟏𝟎−𝟗 m

hc 6.626 x 𝟏𝟎−𝟑𝟒 J s 𝒙 2.998 x 𝟏𝟎𝟖 m𝐬−𝟏
 𝐄𝟑→𝟐 = = = 3.027 x 𝟏𝟎 −𝟏𝟗
J
λ 656.3 x 𝟏𝟎−𝟗 m

 𝐄𝟑→𝟏 = 𝐄𝟑→𝟐 + 𝐄𝟐→𝟏

 𝐄𝟐→𝟏 = 𝐄𝟑→𝟏 − 𝐄𝟑→𝟐 = 1.936 x 𝟏𝟎−𝟏𝟖 J − 3.027 x 𝟏𝟎−𝟏𝟗 J
= 1.633 x 𝟏𝟎−𝟏𝟖 J
hc 6.626 x 𝟏𝟎−𝟑𝟒 J s 𝒙 2.998 x 𝟏𝟎𝟖 m𝐬−𝟏
 λ𝟐→𝟏 = = = 1.216 x 𝟏𝟎 −𝟕
m = 121.6 nm
𝐄𝟐→𝟏 1.633 x 𝟏𝟎−𝟏𝟖 J
The Bohr Atom
- energy of an electron in an atom is quantized.
- Ground state
- Excited state
 The Quantum Mechanical Model of the Atom
- In the Bohr model, electrons are viewed as particles traveling along
circular orbits of fixed radius.
- In the quantum model, electrons are viewed as waves rather than
particles.
- Orbital – region of space to be spread out, delocalized
- Most important similarity between the two models – the energy of
an electron is quantized.
- Diffraction –
- Wave function –
- Schrodinger equation - Hψ = Eψ ( H = operator, E =energy,
ψ = wave function of the electron)
 second order differential equation
ℎ2 𝜕2 ψ 𝜕2 ψ 𝜕2 ψ
 − { + + } + V(𝑥,y,z) ψ = E ψ
8π2 μ 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
 V(𝑥,y,z) – the potential energy
 Schrodinger equation – the total energy as the sum of the kinetic energy
and the potential energy (for any objector particle)
 Potential energy – the most important in describing the structure of atoms
(associated with the coulombic attraction between the positively charged
nucleus and negatively charged electrons as well as the repulsion between
like-charged electrons.
 H𝛙𝐧 = 𝐄𝐧 𝛙𝐧
 𝛙𝐧 - solutions to this equation for an electron in terms of two components:
a radial component, depending only on the distance of the electron from
the nucleus and an angular component, depend on direction or orientation
of the electron with respect to the nucleus
 𝛙𝟐 (positive quantity, the probability of finding an electron at any particular
point)
Orbital – the quantum mechanical equivalent of the location of an
electron

❑Quantum Numbers ( to describe an atomic orbital)

𝛑𝐱
❑In the mathematical terms, ψ(x) = A sin
𝐋
𝟐𝛑𝐱 𝐧𝛑𝐱
❑ ψ(x) = A sin 𝛙𝐧 (x) = A sin ( n = positive integer )
𝐋 𝐋
n = a quantum number
❑Three different quantum numbers
- Principal quantum number (n = 1,2,3,4,5,…….) (shell)
- Secondary quantum number or Subsidiary quantum number or
Azimuthal quantum number ( l = 0,1,2,3,…….(n – 1) )
- Magnetic quantum number ( 𝒎𝒍 = − l, − l+1, − l+2, …, 0 ,+1,+ 2,…., + l )
 The principal quantum number defines the shell in
which a particular orbital is found and must be a positive
integer (n = 1, 2, 3, 4, 5, . . .).

 When n = 1, we are describing the first shell; when n = 2,

the second shell; and so on. Because there is only one
electron in hydrogen, all orbitals in the same shell have
the same energy, as predicted by the Bohr model.

 However, when atoms have more than one electron, the negative
charges on the electrons repel one another. This repulsion between
electrons causes energy differences between orbitals in a shell
 The secondary quantum number - a way to index energy differences between
orbitals in the same shell of an atom.
 The secondary quantum number specifies subshells, smaller groups of orbitals
within a shell.
 When n = 1, the only possible value of l is zero, so there is only one subshell.
When n = 2, l = 0 and l = 1 are both possible, so there are two subshells.
 Each shell contains as many subshells as its value of n.
 s was “sharp,” p was “principal,” d was “diffuse,” and f was “fundamental.”
Beyond f, the letter designations proceed in alphabetical order.

L - value 0 1 2 3 4

Letter designation s p d f g
In the laboratory, it is possible to place atoms in magnetic fields
and observe their spectra. When this is done, some of the emission
lines split into three, five, or seven components. This observation
points to the need for a third quantum number. This index, called
the magnetic quantum number, is labeled 𝑚𝑙 and is also an
integer.
It may be either positive or negative, and its absolute value must
be less than or equal to the value of l for that orbital.
Thus when l = 0, 𝑚𝑙 is also zero.
When l = 1, 𝑚𝑙 may be −1, 0, or +1, and when l = 2, 𝑚𝑙 may be −2,
−1, 0, +1, or +2.
Value Values for l Values for 𝑚𝑙 Number of
of n ( letter orbitals
designation)
1 0 (s) 0 1

2 0 (s) 0 1
1 (p) −1, 0, +1 3

3 0 (s) 0 1
1 (p) −1, 0, +1 3
2 (d) −2, −1, 0, +1, +2 5

4 0 (s) 0 1
1 (p) −1, 0, +1 3
2 (d) −2, −1, 0, +1, +2 5
3 (f) −3, −2, −1, 0, +1, +2, +3 7
 Example 6.5
 Write all of the allowed sets of quantum numbers (n, l, and 𝑚𝑙 ) for
a 3p orbital.
 Solution – 3p orbital - n = 3, l =1 (p orbital)
 Possible values of 𝑚𝑙 = − l to + l
 Therefore, three possible sets of quantum numbers for 3p orbital
 n = 3, l = 1, 𝑚𝑙 = −1
 n = 3, l = 1, 𝑚𝑙 = 0
 n = 3, l = 1, 𝑚𝑙 = +1

 Question – An orbital has quantum numbers of n = 4, l = 2, 𝑚𝑙 = −1. Which type of

orbital ( 1s, …. etc ) is this?
 Visualizing Orbitals
 . The wave function provides information about the probability of finding an orbital
 in a given region of space ( probability of finding electron)
 two –dimensional polar coordinates, a radius (r) and an angle (θ)
 three dimensional polar coordinates, a radius and two angles (θ and Φ)
 Secondary quantum number describes the shape of orbital.
 The s orbital is spherical, whereas the p orbital has two lobes and the d orbital has
four lobes. The two lobes of the p orbital are separated by a plane in which there is
no probability of finding an electron. This plane is called a node or a nodal plane.
The d orbital has two nodes.
Uncertainty principle – it is impossible to determine both the position and
momentum of an electron simultaneously and with complete accuracy.
 How many electrons can occupy an orbital? The introduction of one more quantum
number, spin quantum number (𝑚𝑠 = +1/2 or −1/2)
 n=1 n=2 n=3
4=0 4=0 4=0
ls 3s
2s

The 1s orbital has no nodes. The 2s orbital has one node. The 3s orbital has two nodes.
The Pauli Exclusion Principle – no two electrons in an atom may have the
same set of four quantum numbers.
 If two electrons have the same values for n, l, and ml, then they must have different
spin quantum numbers (ms).
 The major consequence of this principle is that no more than two electrons can
occupy any orbital.
 If two electrons occupy the same orbital, they must be spin paired, one with spin up
and the other with spin down.

Orbital Energies and Electron Configurations

 the size of orbitals tends to increase as the value of n increases.
 the energy of atomic orbitals will increase as the value of the n quantum number
increases.
 . Larger nuclear charges exert stronger attractive forces on electrons, so the size of
the orbitals will tend to decrease for higher atomic numbers.
 For electrons in larger orbitals, therefore, the charge they “feel” is some combination
of the actual nuclear charge and the offsetting charge of electrons located in smaller
orbitals closer to the nucleus.(shielding)
 Instead of interacting with the full nuclear charge, electrons in multielectron atoms
interact with an effective nuclear charge that is smaller than the full charge because of
shielding effects.
 a 2s electron has a greater probability of being found very close to the nucleus, and
an electron closer to the nucleus will experience a larger effective nuclear charge. As
a result, the 2s orbital is lower in energy than the 2p orbitals.
1s

n = 2, = 0

n = 1, = 0 n = 2,

=1

n = 3, = 0
Aufbau principle – this concept resembles constructing a building from
the ground up
Hund’s rule – within a subshell, electrons occupy orbitals individually and
with parallel spins when ever possible.
1s 2s 2p
electron configuration C - 1s2 2s2 2p2

Example 6.6
The presence of sulfur in steel alloys can have a negative effect on ductility
and other properties. So trace analysis is often used to monitor the level of
sulfur present. What is the electron configuration of a sulfur atom?
S - 1s2 2s2 2p6 3s2 3p4
The electrons in the outermost occupied subshells give rise to the
chemical reactivity of an element.

Electrons in filled lower shells will have little impact on an element’s

chemical properties.
The inner electrons, which lie closer to the nucleus, are referred to as core
electrons. They can be represented by the atomic symbol of the noble gas
element that has the corresponding electron configuration.
the complete electronic configuration for potassium is 1s 2 2s 22p6 3s2 3p64s1
the configuration as [Ar]4s1
outer electrons, they are usually referred to as valence electrons
 The Periodic Table and Electron Configurations

 Main group elements – s block

p block
 Transition elements – d block
 Lanthanides and actinides – f block
Periodic Trends in Atomic Properties
 Atomic size
 . There are two ways to explore trends in the periodic table, within a group and within
a period. As we go down a group, we observe an increase in atomic size. As we go
across a period, we observe a decrease
 The size of the atom is determined largely by its valence electrons because they
occupy the outermost orbitals.
 Two factors are important: (1) the shell in which the valence electrons are found and
(2) the strength of the interaction between the nucleus and the valence electrons.
 As we go down a group in the table, the size of the valence orbitals increases with n,
so the size of the atom increases as we go down the column. The trend in moving
across a row is less intuitive.
 The distance between a valence electron and the nucleus will tend to be greater if
there is a small effective nuclear charge
 As we go across a period, we add electrons to the same subshell. These electrons do
not shield each other very well, and the effective nuclear charge increases because
each increment in atomic number adds a positively charged proton to the nucleus.
 The higher effective nuclear charge produces a stronger attraction between the
electrons and the nucleus. So the valence electrons are drawn closer to the nucleus
and the size of the atom decreases
Example 6.9 Using only the periodic table, rank the following elements in order of
increasing size: Fe, K, Rb, S, and Se.
 Atomic radius increases as we go from top to bottom or right to left in the periodic
table. Sulfur and selenium are both in Group 16; because sulfur is above selenium, it
will be smaller. Similarly, the positions of rubidium and potassium in Group 1 tell us
that potassium is the smaller of the two.
 Finally, potassium, iron, and selenium are in the fourth period. Selenium is the
rightmost of the three, so it will be the smallest, followed by iron and then potassium.
Putting all these facts together gives us the requested order: S < Se < Fe < K < Rb
What trend should we expect for the radii of cations and anions?

The loss of an electron to form a cation decreases electron–electron

repulsion, leaving the remaining electrons more tightly bound to the
nucleus. So we would expect positive ions to be smaller than their
respective “parent” atoms.
On the other hand, adding an electron to form an anion will lead to
increased repulsion among the valence electrons. So anions should be
larger than their corresponding neutral atoms.
Ionization energy
 the energy required to remove an electron from an atom, forming a positively
charged cation.
X(g) → X + (g) + e−
 ionization energy varies across periods and within groups of the table.
 across a period, the effective nuclear charge increases, the ionization energy also
generally increases across a period.
 As we move down a group, the valence electrons occupy larger and larger orbitals. As
the valence electrons move farther from the nucleus, they become easier to remove.
So ionization energy decreases as we move down a column in the periodic table.
 I.E. of Oxygen is slightly decrease than that of nitrogen. ( Nitrogen has a half-filled p
subshell, with one electron in each 2p orbital.)
 Similar exceptions to trends are seen for sulfur in the third period and selenium in the
fourth.
Electron Affinity
 electron affinity values can be either positive or negative.
X (g) + e− → X − (g)

Question - A mercury atom emits light at many wavelengths, two of which are at 435.8
and 546.1 nm. Both of these transitions are to the same final state. (a) What is the energy
difference between the two states for each transition? (b) If a transition between the two
higher energy states could be observed, what would be the frequency of the light?
(a)What are the values of azimuthal quantum number for p and f subshells?
i. 2 & 3 ii. 1 & 4 iii. 1 & 3 iv. 2 & 4
(b) What is the shape of the orbital, whose ‘l’ is 1?
i. Spherical ii. Dumb-bell iii. Double dumb-bell iv. Complex
(c) Which of the following is not permissible?
i. n=4, l=3, m=0 ii. n=4, l=2, m=1 iii. n=4, l=4, m=1 iv. n=4, l=0,
m=0
(d) Principal quantum number describes
i. size of the orbital ii. shape of the orbital
iii. spin of the orbital iv. orientation of the orbital
(e) Which atomic orbital is spherical in shape?
i. 3p ii. 2s iii. 3d iv. 4f
(f) When electrons move from a higher energy level to a lower energy level, the
energy is
i. absorbed ii. emitted iii. both i & ii iv. None of these
(g) The maximum number of electrons that can be accommodated in l = 3 is
i. 2 ii. 10 iii. 6 iv. 14

(h) The subsidiary quantum number describes
i. the size of the orbital ii. the shape of the orbital
iii. the spin of the orbital iv. none of these
(i) Which of the following quantum number determines an electron’s spin direction?
i. n ii. ms iii. l iv. m
1. Give the names, symbols and values of the four quantum numbers required to define the
 energy of electrons in the atoms.
2. Draw the box diagram of the electron configuration for each of the following atoms.
i. O atom ii. Mg atom iii. Ar atom
Write values of four quantum numbers for the last added electron for each of the above
atoms.
3. Give the values of four quantum numbers for each electron in the ground state for Be atom.