CHAPTER 2: ELECTRONIC

STRUCTURE OF ATOMS
1. Electronic energy levels of atomic hydrogen
2. Atomic orbitals
3. Electronic configuration
4.Classification of elements into s, p, d and f blocks
in the Periodic Table
(CREDIT CHEW SENSEI)
2.1 Electronic energy levels of
atomic hydrogen
 2.1 (a) Hydrogen’s Emission Spectrum
• A hydrogen discharge tube is a slim tube containing hydrogen gas
at low pressure with an electrode at each end. If you put a high
voltage across this (say, 5000 volts), the tube lights up with a bright
pink glow.
• If the light is passed through a prism or diffraction grating, it is split
into its various colours. What you would see is a small part of the
hydrogen emission spectrum. Most of the spectrum is invisible to
the eye because it is either in the infra-red or the ultra-violet.
• Video related to the topic :
https://www.youtube.com/watch?v=JiKb9jcD0Xs
Extending hydrogen's emission spectrum into
the UV and IR
• There is a lot more to the hydrogen spectrum than the
three lines you can see with the naked eye. It is possible
to detect patterns of lines in both the ultra-violet and infra-
red regions of the spectrum as well.
• These fall into a number of "series" of lines named after
the person who discovered them. The diagram next
shows three of these series, but there are others in the
infra-red to the left of the Paschen series shown in the
diagram.
•
Note: The frequency scale is marked in PHz - that's petaHertz. You are familiar with prefixes like kilo (meaning a thousand or 103 times), and mega (meaning a
million or 106 times). Peta means 1015 times. So a value like 3 PHz means 3 x 1015 Hz. If you are worried about "Hertz", it just means "cycles per second".

This is what the spectrum looks like if you plot it in terms of frequency:
• The Lyman series is a series of lines in the ultra-violet. Notice that
the lines get closer and closer together as the frequency increases.
Eventually, they get so close together that it becomes impossible to
see them as anything other than a continuous spectrum. That's
what the shaded bit on the right-hand end of the series suggests.
• Then at one particular point, known as the series limit, the series
stops.
• If you now look at the Balmer series or the Paschen series, you will
see that the pattern is just the same, but the series have become
more compact. In the Balmer series, notice the position of the three
visible lines from the photograph further up the page.
 The relationship between frequency and wavelength
• The mathematical relationship is:
lambda
(wavelength)
speed
of light 𝐜 = 𝝀𝐟 frequency

• Rearranging this gives equations for either wavelength or frequency.

𝐜 𝐜
𝜆= 𝐟=
𝐟
• What this means is that there is an inverse relationship between the
two - a high frequency means a low wavelength and vice versa.
• This is what the spectrum looks like if you plot it in terms of wavelength instead of
frequency:
 The Balmer and Rydberg Equations
• In 1885 Balmer came up with a simple formula for predicting the
wavelength of any of the lines in what we now know as the Balmer
series. Three years later, Rydberg generalised this so that it was
possible to work out the wavelengths of any of the lines in the
hydrogen emission spectrum.
• What Rydberg came up with was:
λ = wavelength in m
1 1 1 n1 = ground state energy level
= RH 2 − 2
𝜆 n1 n2 n2 = energy level where electron fall from compared to ground state
R H = Rydberg′s constant = 1.097 × 107m−1
• Hydrogen spectrum produced under different sources produce different series with different
characteristics. Table below compare the hydrogen spectrum produced under ultraviolet and
visible ray.
Ultraviolet rays Visible rays
Produced Lyman series Produced Balmer series
Usually use to calculate ionization Can be used to determine wavelength
energy of hydrogen gaseous atom produced by each spectra given by
dispersion of light

Under emission spectrum, electrons from Under emission spectrum, electrons from
higher energy level settled at n=1 higher energy level settled at n=2

Series of convergence lines produced Series of convergence lines produced

have higher frequency have lower frequency
 2.1 (b) The Bohr Model of the Hydrogen Atom
• Niels Bohr, a Danish scientist, explained this line spectrum while
developing a model for the atom:
• The Bohr model shows that the electrons in atoms are in orbits of
differing energy around the nucleus (think of planets orbiting around the
sun).
• Bohr used the term energy levels (or shells) to describe these orbits of
differing energy. He said that the energy of an electron is quantized,
meaning electrons can have one energy level or another but nothing in
between.
• The energy level an electron normally
occupies is called its ground state. But it
can move to a higher-energy, less-stable
level, or shell, by absorbing energy. This
higher-energy, less-stable state is called
the electron’s excited state.
• After it’s done being excited, the
electron can return to its original ground
state by releasing the energy it has
absorbed, as shown in the diagram
below.
• Sometimes the energy released by electrons occupies the portion of
the electromagnetic spectrum (the range of wavelengths of energy) that humans
detect as visible light. Slight variations in the amount of the energy are seen as light
of different colors.
• Neil Bohr outline 3 postulates about hydrogen atom where
a. The Hydrogen atom has only certain allowable energy levels, which Bohr called
stationary states. Each of these states is associated with a fixed circular orbit of the
electron around the nucleus.
b. The atom does not radiate energy while in one of its stationary states (atom does
not change energy while the electron moves within the orbit).
c. The atom changes to another stationary state (the electron moves to another orbit)
only by absorbing or emitting a photon where the energy is equals to the difference
in energy between the two states:
𝐜
𝐄𝐬𝐭𝐚𝐭𝐞 𝐀 − 𝐄𝐬𝐭𝐚𝐭𝐞 𝐁 ∆𝐄 = 𝐡𝐟 𝐨𝐫 ∆𝐄 = 𝐡
𝜆
(where the energy of state A is higher than that of state B, and h is the constant proposed
by Planck’s theory where h = 6.63 x 10-34 Js)
A spectral line results when a photon of specific energy (also specific frequency) is emitted
as the electron moves from a higher energy state to a lower one.
➢ The quantum number, n (where n=1, 2, 3, …) is associated with the “shell” of an
electron orbit, which is directly related to the electron’s energy ( the lower the n
value, the closer the orbit to the nucleus, and the lower is the energy level ).
a)When the electron is in the first orbit (n = 1) , the orbit closest to nucleus, the
hydrogen atom is in its lowest energy level , called the ground state.
b)If the hydrogen atom absorbs a photon whose energy equals the difference
between the first and the second energy levels, the electron moves to the
second orbit (n = 2), the next orbit further from the nucleus. When the
electron is in the second or any higher orbit ( energy level), the atom is said
to be in its excited state. The process where electron moved from ground
state to higher energy level is called as absorption.
c)If the Hydrogen atom in the first excited state ( the electron in the second
orbit) emits a photon of that same energy, it returns to the ground state . The
process where electron dropped from higher energy level (excited state) back
to ground state is called as emission (where radioation will also emit along).
• Figure below shows how Bohr’s model accounts
for the three lines spectra of hydrogen, namely
Lyman series, Balmer series and Paschen series.
When a sample of gaseous Hydrogen atom is
excited, different atoms absorb different
quantities of energy. Each atom has one
electron, but so many atoms are present that all
the energy levels (orbits are populated by
electrons). When the electrons drop from outer
orbits to the n=3 orbit (second excited state),
the emitted photons create the infrared series
of lines. The visible series arises when electrons
drop to the n = 2 orbit ( first excited state).
Figure in next slide shows that the ultraviolet
series arises when electrons drop to the n = 1
orbit (ground state).
a. According to the Bohr model, when an electron
drops from an outer orbit to an inner one, the
atom emits a photon of specific energy that
gives rise to a spectral line. In a given series,
each electron drops and thus each emission,
has the same inner orbit, that is, the same value
of n1 in the Rydberg’s equation, where the
orbit’s radius is proportional to n2 value.
b. An energy diagram shows how the ultraviolet
series arises. Within each series the greater the
difference in orbit radii, the greater the
difference in energy levels and the higher the
energy of the photon emitted. For example, in
the ultraviolet series, in which n = 1, a drop
from n2 = 5 to n1 = 1 emits a photon with more
energy (shorter wavelength, higher frequency)
than a drop from n2 = 2 to n1 = 1.
• One of the usefulness of Bohr’s theory, applied when calculating the
energy levels of atom, which he derived from the classical principle of
electrostatic attraction and circular motion, where the equation is describe
as:
𝐳𝟐
𝐄 = −𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝑱 × Where Z =atomic number; n =energy levels
𝐧𝟐

• For Hydrogen atom, since the atomic number, Z = 1. Therefore:

𝟏
𝐄 = −𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝑱 ×
𝐧𝟐
• If the ground level (under Lyman series) n = 1, the energy at ground state is

𝟏
𝐄 = −𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝑱 × 𝐄 = −𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝐉
𝟏𝟐 thus
• This equation will then further derive from Rydberg’s equation and
Planck’s equation, where Planck’s equation can be written as

𝟏
𝐄 = 𝒉𝒇 𝐨𝐫 𝑬 = 𝐡 × 𝐜 ×
𝝀
E = energy transition
h = 6.63 x 10−34 Js (Planck′s constant)
c = 3.00 x 108ms−1(speed of light)
R H = Rydberg′s constant = 1.097 × 107m−1
• Substituting the constant value in the equation

𝟏 𝟏
𝐄 = 𝐡 × 𝐜 × 𝐑𝐇 𝟐 − 𝟐
𝐧𝟏 𝐧 𝟐

𝟏 𝟏
𝐄 = 𝟔. 𝟔𝟑 𝐱 𝟏𝟎−𝟑𝟒 × 𝟑. 𝟎𝟎 𝐱 𝟏𝟎𝟖 × 𝟏. 𝟎𝟗𝟕 × 𝟏𝟎𝟕 −
𝐧𝟏𝟐 𝐧𝟐𝟐

𝟏 𝟏
𝐄 = 𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝐉 × −
𝐧𝟏𝟐 𝐧𝟐𝟐
Examples
1. Calculate the wavelength, expressed in nm, of the following conditions
a) The first line in Lyman series b)The third line of Balmer series
In Lyman series, n1 =1, question ask first line in series, In Balmer series, n1 = 2, question ask third
so n2 = 1+1 = 2 line in series, so n2 = 2+3 = 5
1 1 1 1 1 1 1 1
= R H 2 − 2 = 1.097 × 107 2 − 2 7 1 1
𝜆 n n 1 2 = R H 2 + 2 = 1.097 × 10 −
1 2 𝜆 n1 n2 22 52
λ = 1.2154 × 10−7𝑚 = 122 𝑛𝑚
λ = 4.341 × 10−7𝑚 = 434 𝑛𝑚

c)The fourth line of Paschen series d)The last line of Balmer series
In Paschen series, n1 =3,question ask fourth line in In Balmer series, n1 = 2, question ask last line in
series, so n2 = 3+4 = 7 series so n2 = 2+∞ = ∞
1 1 1 1 1
= R H 2 − 2 = 1.097 × 107 2 − 2
𝜆 n n 3 7
1 2

λ = 1.005 × 10−6𝑚 = 1005 𝑛𝑚

2. Calculate the frequency produced from the below spectra

a)The second line of Paschen series b)The last line of Lyman

In Paschen series, n1 =3, question ask second line in series In Lyman series, n1
series, so n2 =3+2 =5 = 1,
1
1 1 1 𝑓=𝑐× question ask last line in series, so n2 = 1+∞ = ∞
= RH 2 − 2 𝜆 1 1 1 1
𝜆 n1 n2 = RH 2 − 2 𝑓 = 𝑐 ×
𝑓 = 3.00 × 108 ms−1 𝜆 n n 𝜆
1 1 1 2
1 1
= 1.097 × 107 − × (7.80 × 105)m−1
3 2 5 2 = 1.097 × 107 2 − 2 𝑓 = 3.00 × 108 ms−1
1 ∞ × (1.097 × 107)m−1
= 7.80 × 105m−1 = 2.34 × 1014s−1
= 1.097 × 107m−1 = 3.29 × 1015s−1
c) The third line of Lyman series d) The fifth line of Balmer series
3. Using Bohr’s equation, calculate the energy required to cause the emission of spectral line below

a) The fifth line of Lyman series b)The first line of Balmer series
In Lyman series, n1 =1, question ask fifth line in series, In Balmer series, n1 =2, question ask fifth line in series,
So n2 =1+5 =6 −18 So n2 =2+1 =3 1 1
∆E = 2.18 × 10 J × 1 − 1 ∆E = 2.18 × 10−18J × 2 − 2
n12 n22 n1 n2
1 1 1 1
= 2.18 × 10−18J × − = 2.18 × 10−18J × −
12 62 22 32
= 2.12 × 10−18J/e− = 3.03 × 10−19J/e−
c) The third line of Paschen series d) The last line of Paschen series
Using the spectrum to find hydrogen's ionisation energy
• When there is no additional energy supplied to it, hydrogen's electron is found at
the 1-level. This is known as its ground state. If you supply enough energy to
move the electron up to the infinity level, you have ionised the hydrogen.
• The ionisation energy per electron is therefore a measure of the distance
between the 1-level and the infinity level. If you look back at the last few
diagrams, you will find that that particular energy jump produces the series limit of
the Lyman series.
• If you can determine the frequency of the Lyman series limit, you can use it to
calculate the energy needed to move the electron in one atom from the 1-level to
the point of ionisation. From that, you can calculate the ionisation energy per
mole of atoms.
• The problem is that the frequency of a series limit is quite difficult to find
accurately from a spectrum because the lines are so close together in that region
that the spectrum looks continuous.
•
• So how do we determine the ionisation energy (the energy needed in order to remove one
mole of electron from an atom in gaseous state)of hydrogen atom?

• In order to remove the electron from hydrogen atom, the electron must reach the limit of the
energy level n =∞.

• Remember the ground state energy level of Lyman series is n =1. Thus to find the difference
of energy level using Bohr’s equation is stated as below:
1 1
∆E = 2.18 × 10−18J × −
n12 n22
1 1
∆E = 2.18 × 10−18J × 2 − 2
1 ∞

∆E = 2.18 × 10−18J
1kJ
For 1 mol e- , ∆H = E × NA ×
103J 1kJ
∆H = 2.18 × 10−18J × 6.02 × 1023 × 3
10 J
∆H = 1310 kJmol −1
• To remove 1 mol of electron from ground state, n1 =1 to convergence limit, n2 =∞,a total of
1310 kJ is required.