Atomic Structure

Chapter 2

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 2

2.1
Properties of Waves and
Hydrogen Spectrum

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 Properties of Waves

Wavelength () is the distance between identical points on

successive waves.
Amplitude is the vertical distance from the midline of a
wave to the peak or trough.
Frequency () is the number of waves that pass through a
particular point in 1 second. (Hz = 1 cycle/s).

The speed (u) of the wave =  x  3

Maxwell (1873), proposed that visible light consists of
electromagnetic waves.

Electromagnetic
radiation is the
emission and
transmission of
energy in the form
of electromagnetic
waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s

All electromagnetic radiation
x=c 4
5
Calculate the speed of a wave whose wavelength
and frequency are 17.4 cm and 87.4 Hz respectively.

The wavelength of the green light from a traffic signal

is centered at 522 nm. What is the frequency of this
radiation?

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“Black Body Problem” : Solved by Planck in 1900

Energy (light) is emitted or absorbed

in discrete units (quantum).

E=hx
Planck’s constant (h)
h = 6.63 x10-34 J•s

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“Photoelectric Effect” : Solved by Einstein in 1905

Photon is a “particle” of light

Light consisted of stream of particles, called photons.

Each photon carried energy E= h,

h=Planck's constant,
=frequency of light.

Light has both:

1. wave nature
2. particle nature
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Continuous spectrum consists of whole series of
electromagnetic wavelengths with no gaps.

Lines spectrum consists of a series of electromagnetic

radiation at specific wavelength.

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A photon has a frequency of 6.0 x104 Hz. Convert This
frequency into wavelength (nm). Does this frequency
fall in the visible region?

x=c
 = c/
= 3.00 x 108 m/s / 6.0 x 104 Hz
= 5.0 x 103 m
= 5.0 x 1012 nm

Radio wave

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Calculate the energy of a photon with a wavelength
of 5.00 x104 nm.

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 Hydrogen Spectrum

Line Emission Spectrum of Hydrogen Atoms

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• H2 gas is placed in a discharge tube containing 2
electrodes.
• As electrons flow from –ve electrode to +ve electrode,
they collide with the H2 gas, breaking molecules into
atoms. The Hydrogen atoms absorb energy and become
excited.
• The electrons will then jump to a higher energy level.
When the electrons return to lower energy level, excess
energy is given out as light.
• The emitted light is separated into its components by a
prism. Each component is focused according to its
wavelength and then formed a line (a coloured image).

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• The separated components is found to contain separate
sets of lines. Each set of lines is called a series.
• In each series, the differences between the lines become
smaller and smaller towards the low wavelength and
high frequency of the spectrum.
• Lyman series - spectra lines in the uv area.
• Balmer series - spectra lines in the visible light region.
• Paschen series - spectra lines in the infrared region.
• Brackett series - spectra lines in the infrared area.
• Quantum theory uses the information to explain spectra
and the position of electrons in atoms by absorbing and
releasing energy.
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 15

2.2
Bohr’s Atomic Model and
Rydberg Equation

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Bohr’s atomic model states the following:
1. Electron can only have
specific (quantized) energy
values.

2. Light is emitted as electron

moves from one energy
level to a lower energy
level.
∆E = E1 - E2
1 1
= RH ( )
ni2 nf 2

n (principal quantum number) = 1,2,3,…

RH (Rydberg constant) = 2.18 x10-18 J OR 1.097 x107 m-1
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If an electron jumps from a higher energy level ni with
energy Ei to a lower energy level nf with energy Ef, the
difference in energy, E= Ef - Ei
Energy level diagram
since
( 1 )
Ef = -RH 2 and
n
f

( 1 )
Ei = -RH 2
ni

Ephoton = E = Ef - Ei
1 1)
E = RH 2
(
n n2
i f 17
The values of ni and nf in the Rydberg equation for
different series in the hydrogen emission spectrum are
listed in the following table.

Series nf ni 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

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 Calculate the wavelength (in nm) of a photon emitted
by a hydrogen atom when its electron drops from the
n = 5 state to the n = 3 state.

Ephoton = E
1 1
= RH ( 2 )
ni n2f
= 2.18 x 10-18 J x (1/25 - 1/9)
= -1.55 x 10-19 J

Ephoton = h x c / 
 = h x c / Ephoton
= 6.63 x10-34 (J•s) x 3.00 x108 (m/s) / 1.55 x10-19J
= 1280 nm 19
 20

2.3
Atomic Orbital and
Quantum Numbers

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 Schrodinger Wave Equation

In 1926 Schrodinger wrote an equation that described both

the particle and wave nature of the electron.

Wave function () describes:

1. energy of electron with a given 
2. probability of finding electron in a volume of space.

Schrodinger’s equation can only be

solved exactly for the hydrogen atom.
Must approximate its solution for multi-
electron systems.
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7.5
Shell – referred to energy level, n =1,2,3…
– locates electrons with the same value of n.

Subshell – sub division of shell, named s, p, d, f

n=1, there is only 1 subshell: s
n=2, there are 2 subshells: s, p
n=3, there are 3 subshell: s, p, d
– contains electrons with the same values of n
and l.

Orbital – space which electron can be found

– each subshell contains orbital
– contains electrons with the same values of n, l,
and ml.
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 Schrodinger Wave Equation
 = fn(n, l, ml, ms)

principal quantum number n

n = 1, 2, 3, 4, ….

distance of e- from the nucleus

n=3
n=2
n=1

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 Schrodinger Wave Equation
 = fn(n, l, ml, ms)

angular momentum quantum number l

for a given value of n, l = 0, 1, 2, 3, …. n-1

n = 1, l = 0 l=0 s orbital
l=1 p orbital
n = 2, l = 0 or 1
l=2 d orbital
n = 3, l = 0, 1, or 2 l=3 f orbital

shape of the “volume” of space that the e- occupies

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Orbitals - shapes

l = 0 (s orbitals)

l = 1 (p orbitals)

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l = 2 (d orbitals)

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 Schrodinger Wave Equation
 = fn(n, l, ml, ms)

magnetic quantum number ml

for a given value of l

ml = -l, …., 0 , …. +l

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

orientation of the orbital in space

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3 orientations is space

ml = -1 ml = 0 ml = 1

5 orientations is space

ml = -2 ml = -1 ml = 0 ml = 1 ml = 2
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 Schrodinger Wave Equation
 = fn(n, l, ml, ms)
clockwise anti-clockwise

spin quantum number ms

ms = +½ or -½

ms= +½ ms= -½

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 Schrodinger Wave Equation
 = fn(n, l, ml, ms)

Existence (and energy) of electron in atom is described by

its unique wave function .

Pauli exclusion principle - no two electrons in an atom

can have the same four quantum numbers.

Each seat is uniquely identified

(E, R12, S8)
Each seat can hold only one
individual at a time
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 How many 2p orbitals are there in an atom?

n=2 If l = 1, then ml = -1, 0, or +1

2p 3 orbitals

l=1

How many electrons can an orbital hold?

If n, l, and ml are fixed, then ms = ½ or - ½

 = (n, l, ml, ½) or  = (n, l, ml, -½)
An orbital can hold 2 electrons
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How many electrons can be placed in the 3d
subshell?

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List the values of n, l and ml for orbitals in the
4d subshell.

n
l
ml

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 34

2.4
Electron Configuration

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Electron configuration is how the electrons are
distributed among the various atomic orbitals in an atom.

number of electrons in
the orbital or subshell
1s1
principal quantum angular momentum
number, n quantum number, l

Orbital diagram is a diagram showing the arrangement

of electron in each of its orbitals.

H
1s1 35
Electron Configurations of Elements

n=3 l = 2

n=3 l = 1
n=3 l = 0
e- in n=2 or higher
n=2 l = 1 is in excited state
n=2 l = 0

ground state:
n=1 l = 0 lowest energy,
most stable state
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Aufbau principle - “Fill up” electrons in lowest
energy orbitals.

C 6 electrons C 1s22s22p2
B 5 electrons B 1s22s22p1
Be 4 electrons Be 1s22s2
Li 3 electrons Li 1s22s1
He 2 electrons He 1s2
H 1 electron H 1s1
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Hund’s rule - The most stable arrangement of
electrons in sub-shells is the one with the greatest
number of parallel spins.

Ne 10 electrons Ne 1s22s22p6
F 9 electrons F 1s22s22p5
O 8 electrons O 1s22s22p4
N 7 electrons N 1s22s22p3
C 6 electrons C 1s22s22p2

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 Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
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Abbreviated Electron configuration – an arrangement
where noble gas symbol is used to represent the inner
shell and the valence shell is written after it.
It is used to highlight the valence electrons, those
involved in bonding.

e.g. Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s

1s22s22p63s2
Abbreviated as [Ne]3s2 [Ne] :1s22s22p6

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 Paramagnetic Diamagnetic
Paramagnetic substances are those Diamagnetic substances do not
that contain net unpaired spins and contain net unpaired spins and
are attracted by a magnet. are slightly repelled by a magnet.

unpaired electrons all electrons paired

2p 41
2p
 Electron Configurations of Ions

• When atoms lose or gain electrons they achieve noble

gas e- structure.

• Metals lose valence e-’s.

e.g. Na → Na+
Na : 1s22s22p63s1
Na+ : 1s22s22p6

• Non-metals gain e-’s.

e.g. Cl → Cl-
Cl : 1s22s22p63s23p5
Cl- : 1s22s22p63s23p6
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Na [Ne]3s1 Na+ [Ne]
Atoms lose electrons so
Ca [Ar]4s2 Ca2+ [Ar] that cation has a noble-gas
outer electron configuration.
Al [Ne]3s23p1 Al3+ [Ne]

Atoms gain H 1s1 H- 1s2 or [He]

electrons so that
anion has a noble- F 1s22s22p5 F- 1s22s22p6 or [Ne]
gas outer electron
configuration. O 1s22s22p4 O2- 1s22s22p6 or [Ne]

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Electron Configurations of d-block Elements

• Transition elements always lose their 4s electrons first

and they can lose more than 2 electrons.
e.g. 1s22s22p63s23p64s23d6 or [Ar]4s23d6
26Fe

Fe+ 1s22s22p63s23p64s13d6 or [Ar]4s13d6

Fe2+ 1s22s22p63s23p64s03d6 or [Ar]4s03d6

Fe3+ 1s22s22p63s23p63d5 or [Ar]3d5

When a cation is formed from an atom of a transition

metal, electrons are always removed first from the ns
orbital and then from the (n – 1)d orbitals.
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 Exceptions
Half-filled or completely filled d subshells have greater stability

24Cr 1s22s22p63s23p6 3d5

4s1
_____ _
The electron is placed in a 3d orbital
so that the 3d orbitals are half-filled.
NOT 1s22s22p63s23p63d44s2

29Cu 1s22s22p63s23p6 3d10 4s1

_____ _
NOT 1s22s22p63s23p63d94s2 45
What is the electron configuration for
Br, K+, Ni2+, Zn2+, N3-

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An oxygen atom has a total of eight electrons.
Write the four quantum numbers for each of the
eight electrons in the ground state.

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