CHAPTER 3

ATOMIC STRUCTURE

1
At the end of the chapter students will be able to:

1. Solve problem using Rydberg Equation.

2. Determine the Quantum Numbers for orbital.
3. Explain the meaning of orbital symbols.
4. Draw and write orbital diagram and electronic configuration
using correct principle.

2
1. Subatomic particles
Proton
Neutron
Electron

2. Atomic symbol
Element symbol
Atomic number
Mass number

3. Isotope

3
 Visible and invisible light (or radiation) are all known as
electromagnetic radiation.

 Electromagnetic (EM) radiation travel in waves and

defined by their wavelength (λ) and frequency (v)

c=λν c = speed of light

= 3.0 x 108 ms-1

 Radiation with a high frequency has a short wavelength,

vice versa.

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Properties of Waves

 Frequency (v) is the number

of cycles the wave undergoes
per second. Unit is 1/second
or (s-1) (Hertz)

 Wavelength (λ) is the

distance of the wave travels
during one cycle. Units is
nanometer (nm), picometer
(pm) or Armstrong (Å)

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• Amplitude of an EM wave is a
measure of the strength of its
electric and magnetic fields

• Related to the intensity of the

radiation ~ brightness
 Lower amplitude
(dimmer)
 Higher amplitude (brighter)

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 I
Y

p
B
R

G
O

wavelength
7

frequency
 Invisible light (cannot be seen with the naked eye)
include gamma rays, X-rays, ultra-violet, infra-red and
microwave

 Visible light such as white light, separates into a

continuous spectrum of colors when it passes through a
prism. Exist at λ = 400 - 750 nm

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 When elements (e.g. Na, He) are used as a source of
light, a characteristic line spectrum is observed.

 Quantum theory states that light is emitted in the form of

a ‘discrete’ or definite packet called ‘quantum’.

 The frequency of light, ν is proportional to the energy, E.

ΔE = hν

where, h = 6.63 x 10-34 J s (Planck constant)

9
Niels Bohr’s Atomic Model (1913)
 Electrons exist in a series of shells and has specific energy
levels
 Orbit about the nucleus much like the way planets orbit the
sun
 Energies of electrons are quantised
 Energy of an electron in a given shell:

 1 
En   RH  2 
n 
Where RH is the Rydberg’s constant (2.18 x 10-18J),
n is quantum number (n=1,2,3…..)
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 Electron nearest to nucleus has the lowest energy and most
stable state = ground state
 Electron absorb energy (absorption) → the electron is
elevated to a higher energy level (excitation) → excited state
 Electron releases energy (emission) → the electron falls
from its excited state to ground state of a lower energy level.
Energy released shows up as line spectrum
 Characteristics of line spectra used to determine the
electronic structure of atom

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• Line Spectrum of Atomic Spectrum
Line spectrum consist of discrete lines of different
wavelengths (discontinuous spectrum)

 Emission Spectrum
Produced by heating atomic vapour → electron
excited → unstable → falls to lower energy level →
light emit →pass through prism → series of
wavelength lines

 Absorption Spectrum
Produced by passing the white light from a
source through the unexcited sample that
absorbs certain wavelength of light →dark lines
appear on the continuous bright background
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 An electric discharge is passed through a gas discharge
tube containing hydrogen.

 The high energy electrons from the negative electrode to

positive electrode collide with the H2 molecules.

 This causes the H2 molecules to dissociate into H atoms

and the tube emits light.

 When the emitted light is passed through a prism, the light

is dispersed and separated into its components

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14
 Transitions of electrons between two energy levels
produce lines.

 There are several emission series of lines obtained during

the transition and are classified according to which level
the electrons drop to.

Series n1 n2 Spectrum region

Lyman 1 2,3,4… Ultraviolet
Balmer 2 3,4,5… Visible
Paschen 3 4,5,6… Infrared
Brackett 4 5,6,7… Infrared
Pfund 5 6,7,8… Infrared
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Transitions of electrons (from n1 to n2) which produce the
lines in each series

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• If the electron jumps for higher energy level (n2) with E2
to a lower energy level (n1) with energy E1, the difference
in energy (∆E) is given by the equation:

1 1
E  E2  E 1 h   R ( 2  2 )
H n2 n1

RH = Rydberg’s constant (2.18 x 10-18 J)

n = energy levels (n2>n1)

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 The wavelength (λ ) of every line in the hydrogen
spectrum is determine by equation:

1 1 1
 R ( 2  2 )
 H n2 n1

λ = wavelength
RH = Rydberg’s constant (1.097x 107 m-1)
n = energy levels (n2>n1)

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 SAMPLE PROBLEM
If the electron of hydrogen atom had initially been in its 6th
Bohr’s orbit, determine the frequency of the EM radiation
emitted if it forms a line spectrum in the Paschen series.

SOLUTION:

n1= 3, n2= 6
1 1 1
 R ( 2  2 )
 H n2 n1
 1 1  -1
 1.097  10  2  2 m
7

6 3 
 914166.67m 1
c
  
   3.00 108 ms -1 914166.67m 1  2.74 1014 s 1
 19
 SAMPLE PROBLEM
A hydrogen atom absorbs a photon of visible light and its
electron enters the n = 4 energy level. Calculate
(a) the change in energy of the atom
(b) wavelength and convert to nm
SOLUTION:
(a) n1 = 2, n2 = 4, RH = 2.18 x 10-18 J

 1 1 
E   RH 
 n2  n2 

 2 1 

1
18 1
E  2.18  10 J ( 2  2 )
4 2
1 1
E  2.18  10 18 J (  )
16 4
E  4.09  10 -19 J 20
SOLUTION:

(b) wavelength and convert to nm

c
E  hv  h

c 6.63 x 10 -34 J s  3.0 x 108 ms -1
h 
E 4.09  10 -19 J
  4.86  10 7 m
 486 nm

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An atomic orbital is specified by FOUR quantum numbers.

n, the principal quantum number - a positive integer

l, the angular momentum quantum number - an integer from 0 to n-1

ml , the magnetic moment quantum number - an integer from -l to +l

Three quantum numbers are required to describe the distribution of

electrons in hydrogen and other atoms.

s, electron spin

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Symbol Quantum number Description

n Principle Energy level

Azimuthal or angular
ℓ Shape of orbital
momentum

m Magnetic Orbital orientation in space

Direction that the electron
s Electron spin spins; clockwise or
anticlockwise

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 Symbol – n

 Describes the shell or energy level

 Values – positive integer (1,2,3,4…..∞)

 Example:
 n = 1(the shell closest to the nucleus, lowest energy)
 n = 4 (the 4th shell)

 The higher the value of n, the higher is the energy of

the shell
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 n

4
n can be a

energy
3
size

2 positive integer
(1,2,3,…)
1

• n describes the coarse energy and size of the electron

orbital.

• relates to the average distance of the electron from the

nucleus.

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 Symbol – l
 Specifies a subshell in an atom
 Values: n-n…up to…n-1
 Example:
 When n = 1, l = (1-1) = 0
 When n = 2, l = (2-2), (2-1) = 0,1
 When n = 3, l = (3-3), (3-2), (3-1) = 0,1,2

Note that the number of possible l values equals the

value of n
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• The values of l, are related to names or orbitals or
letter codes for subshells:
value of l orbital name
(subshell letter code)
0 s
1 p
2 d
3 f
4 g
• To name a particular orbital (or subshell), we combine
the value of n followed by the letter code for the
subshell

• E.g. The subshell with n = 3 and l = 1 is the 3p orbital

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 l tell us the “shape” of the orbitals

 l can be zero or a positive integer

 l = ( 0 , 1 , 2 , 3 , 4 …, n-1)

s p d

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 Symbol - ml

 Describes the orientations (or components) of orbitals

relative to each other

 Values: - l ….0…..+ l

 For example:
 when l = 1, ml = -1, 0, +1
 when l = 2, ml = -2,-1, 0, +1, +2

 Degenerate orbitals (orbitals of similar energy). Each

components are represented by subscripts (e.g. Px, Py,
Pz..). 29
  ml indicates the orientation of the electron’s orbital with
respect to the three axes in space.

for l = 1

ml = -1 ml = 0 ml = +1

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Symbol – s

Describes the direction in which the electron spins on its axis

Values:
 ms = +½ (e- spins in clockwise direction, ↑)
 ms = -½ (e- spins in anticlockwise direction, ↓)

Only 2 electrons may occupy each one ‘orbital orientation’

and the electrons must have opposite spins

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• Possibilities for electron spin:

N
S

e-
e-

S
N

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Quantum number for the first four levels of orbitals:

n l ml Orbital No. of
designation orbitals
1 0 0 1s 1
2 0 0 2s 1
1 -1,0,+1 2p 3
3 0 0 3s 1
1 -1,0,+1 3p 3
2 -2,-1,0,+1,+2 3d 5

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Relationship among quantum number:

Each shell can be filled with 2n2 electrons and each subshell
can be filled by 2(2l + 1) electrons.

For example:

The 4th shell (n=4) is filled by (2 x 42) = 32 e-

each 4s subshell is filled by 2[2(0) + 1] = 2e-

each 4p subshell is filled by 2[2(1) + 1] = 6e-
each 4d subshell is filled by 2[2(2) + 1] = 10e-
each 4f subshell is filled by 2[2(3) + 1] = 14e-

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 Summary of Quantum Numbers of Electrons in Atom

Name Symbol Permitted values Property

Principal n +ve integers (1,2,3..) orbital energy (size)

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

Magnetic ml integers from –l to 0 to +l orbital orientation

Spin ms +1/2 or -1/2 direction of e- spin

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l = 0 (s orbitals)

l = 1 (p orbitals)

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l = 2 (d orbitals)

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SAMPLE PROBLEM:
What values of the angular momentum (ℓ) and magnetic (m)
quantum numbers are allowed for a principal quantum
number (n) of 3? How many orbitals are allowed for n = 3?
PLAN: Follow the rules for allowable quantum numbers found in the text.
ℓ values can be integers from 0 to n-1; m can be integers from -ℓ
through 0 to +ℓ

SOLUTION: For n = 3, ℓ = 0, 1, 2
For ℓ = 0 m = 0
For ℓ = 1 m = -1, 0, or +1
For ℓ = 2 m = -2, -1, 0, +1, or +2
There are 9 m values and therefore 9 orbitals with
n = 3.
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SAMPLE PROBLEM:
Give the name, magnetic quantum numbers,
and number of orbitals for each sublevel with the
following quantum numbers:

(a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l =3

SOLUTION:
n l sublevel possible ml No of
name values orbitals
(a) 3 2 3d -2, -1, 0, 1, 2 5
(b) 2 0 2s 0 1
(c) 5 1 5p -1, 0, 1 3
(d) 4 3 4f -3, -2, -1, 0, 1, 2, 7
3
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SAMPLE PROBLEM
State the orbitals and maximum number of electrons that
can occupy each orbital for each of quantum numbers given
below
(a) n = 6, ℓ = 0 (b) n = 4, ℓ = 2 (c) n = 5, ℓ = 1
SOLUTION:

Orbital Maximum no. of electron

6s 2

4d 10

5p 6

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 Electronic Configurations
 Describe how electrons are distributed among various
orbitals in the principle shell (n) and subshell of an atom (ℓ)

 Quantum numbers are used to describe electron

configuration

 Each main shell accommodate 2n2 electrons

 Various way to indicate arrangement of electron in atom

 Dart board
 Orbital diagram
 “spdf” notation

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Electronic Configurations

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43
 Arrangement of Electron
Three rules for assigning electrons:

 Aufbau Principle

 Pauli Exclusion Principle

 Hund’s Rule

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 1. Aufbau Principle
Electrons fill the lowest energy level subshell first before
moving to the next level (with higher energy)

Aufbau = ‘building up’

The energy of orbitals

increase as follows:

1s < 2s < 2p < 3s < 3p < 4s

< 3d < 4p < 5s < 4d< 5p <
6s < 4f <5d < 6p < 7s < 5f <
6d < 7p < 8s …
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2. Pauli Exclusion Principle
A maximum of two electrons can occupy each
orbital. Each electron must have different spin
quantum numbers

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 3. Hund’s Rule
• The most stable arrangement of electrons is that with the
most unpaired electrons all with the same spin.

• The rule states that when entering orbitals of identical

energy, electrons initially occupy them singly and with the
same spins, that is, with parallel spins

• Once all the orbitals are singly occupied, subsequent

electron occupation will start to result in them pairing up

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Ground-state electron configurations

First three period

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SAMPLE PROBLEM Determining Electron Configuration

Using the periodic table, give the full and condensed electrons
configurations, partial orbital diagrams showing valence electrons, and
number of inner electrons for the following elements:

(a) potassium (K: Z = 19) (b) molybdenum (Mo: Z = 42) (c) lead (Pb: Z = 82)
PLAN: Use the atomic number for the number of electrons and the periodic
table for the order of filling for electron orbitals. Condensed
configurations consist of the preceding noble gas and outer electrons.
SOLUTION:
(a) for K (Z = 19)

full configuration 1s22s22p63s23p64s1

condensed configuration [Ar] 4s1

partial orbital diagram There are 18 inner electrons.

4s1 3d 4p
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(b) for Mo (Z = 42)
full configuration 1s22s22p63s23p64s23d104p65s14d5
condensed configuration [Kr] 5s14d5
partial orbital diagram There are 36 inner electrons
and 6 valence electrons.

5s1 4d5 5p

(c) for Pb (Z = 82)

full configuration 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p2

condensed configuration [Xe] 6s24f145d106p2

partial orbital diagram

There are 78 inner electrons

and 4 valence electrons.
6s2 6p2

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 Ion & Isoelectronic Configurations
Aluminium (Al) : 1s22s22p63s23p1

Aluminium ion (Al3+) : 1s22s22p6

 Isoelectronic = different species having same electron

configuration

O2- : 1s22s22p6
F- : 1s22s22p6
Ne : 1s22s22p6

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52
 Electron configurations of Chromium and Copper

Cr: 1s2 2s2 2p6 3s2 3p6 3d5 4s1 or [Ar] 3d5 4s1

↑ ↑ ↑ ↑ ↑ ↑

3d 4s

Cu: 1s2 2s2 2p6 3s2 3p6 3d10 4s1 or [Ar] 3d10 4s1

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

3d 4s
NOTE
d subshells that are half-filled or fully
filled are particularly stable compare
with partially filled orbitals

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54
55
SAMPLE PROBLEM
Write the electronic configurations of S2-, Ni(II) and Fe(III)
SOLUTION:

a) S = 16 electrons
S2- = (16 + 2 ) electrons = 18 electrons = 1s2 2s2 2p6 3s2 3p6

b) Ni = 28 electrons
Ni2+ = (28 - 2) electrons = 26 electrons = 1s2 2s2 2p6 3s2 3p6 3d8

c) Fe = 26 electrons
Fe3+ = (26 - 3) electrons = 23 electrons = 1s2 2s2 2p6 3s2 3p6 3d5

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 Paramagnetic substance
– Those that contain net unpaired spins and are
attracted by a magnet

 Diamagnetic substance
– Those that do not contain net unpaired spins are
slightly repelled by a magnet
– Electron spins are paired, or antiparallel to each other,
(↑↓) or (↓↑)

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 Paramagnetic Diamagnetic

unpaired electrons all electrons paired

2p 2p
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PROBLEM:

Use condensed electron configurations to write the reaction for the

formation of each transition metal ion, and predict whether the ion is
paramagnetic.

(a) Mn2+(Z = 25) (b) Cr3+(Z = 24) (c) Hg2+(Z = 80)

Solution:
(a)Mn2+ (Z = 25) Mn ([Ar] 4s23d5) Mn2+ ([Ar] 3d5) + 2e−

paramagnetic

(b) Cr3+(Z = 24) Cr ([Ar] 4s13d5) Cr3+ ([Ar] 3d3) + 3e−

paramagnetic

(c) Hg2+(Z = 80) Hg ([Xe] 6s24f145d10) Hg2+ ([Xe] 4f145d10) +2e−

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diamagnetic