Atomic Structure and

the periodic table-2

CAPE Chemistry-Unit 1

Objectives
Explain

how data from emission

spectra provide evidence for
discrete energy levels within the
atom
Describe the atomic orbitals
Describe the shapes of the s and
p orbitals
Determine the electronic
configurations of atoms and ions
in terms of s, p and d orbitals

Testing Rutherfords Model of the

Atom
If

the nucleus is positively charged and the

electrons are negatively charged.
What then stops the electrons from being pulled
into the nucleus by electrostatic attraction?

According

to the laws of classical physics,

the electrons orbiting the positive nucleus
would gradually lose energy and be pulled
into the nucleus.
This would effectively cause the collapse of
the atom.
Why does this not happen?

Electrons in Atoms
Modern

theory of the atom rests on the fact that

atoms can emit light if they have absorbed energy
i.e. become excited.
The wavelength of the light absorbed is characteristic of
the element concerned.

Why

do different atoms have different chemical

properties?

If

all atoms are composed of the same components,

then what is it that makes one atom different from
one another?
The answer is due to the number and arrangement of the
electrons, i.e. the atoms electronic configuration.

Atomic Spectra
Isaac

Newton showed that

sunlight composed of many
colours.

When

sunlight or light from an

electric bulb is passed through
a prism onto a screen, a
rainbow of colours in seen.

The

spectrum of colours is
called a continuous
spectrum

Light

of all visible wavelength

is called white light

Form of Radiant Energy

Radiant

energy comes in many

forms

Visible light
Infrared radiation
UV radiation
Microwaves etc.

Collectively

they make up the

electromagnetic spectrum

Electromagnetic Radiation
(EMR)

Wave Nature of EMR

Electromagnetic radiation behaves like waves in the ocean when
travelling thru a vacuum.
Electromagnetic radiations are characterized by their frequencies and
wavelengths.

Electromagnetic Radiation
Electromagnetic

radiation (EMR)

Frequency (): s-1 (Hz)

Wavelength (): m or nm

Or

= c/
= c/

Energy of radiation, E=h

(Plancks constant) h = 6.626 1034 J
s.
Speed of light, C = 3.0 x 108 ms-1

Question
The

light blue glow given off by

mercury lamps has a wavelength of
436 nm. What is its frequency?

What

is the wavelength (in meters) of

an FM radio wave with frequency, =
102.5 MHz and a medical X ray with
frequency, = 9.55 x 1017 Hz?

EMR and Atomic Spectra

If

atoms are heated or excited

energetically, they emit light of
certain wavelengths. The
spectrum observed is a number
of coloured lines against a black
background.
This spectrum is called the
atoms emission spectrum or
line spectrum

Atomic Spectra
All

substances produce an emission

spectrum when they are excited whether
by heat energy or electrical energy.

The

emission (and absorption) spectra of

atoms give us an understanding of the
arrangement of electrons within the
atom.

Each

atom has a unique emission or

absorption spectra.

Atomic Emission-Line Spectra of

Hydrogen

Questions that need

answering!!!
Why

do atomic spectra consists

of discrete (separate) lines.

Why

do atoms absorb or emit

light of certain frequencies?
Rutherford model does not account
for these observations

Hydrogen absorption/emission
spectra

The Bohr Model of the

atom
This

model aimed to explain the

observation that EMR emitted by an
excited atom has specific energies.
Electrons are in circular orbits of fixed
or quantised energy.
They will not absorb or emit energy as long
as they stay within this orbit.
Therefore

the energy of the electron in

an atom must also be quantised..i.e..an
electron can only have certain discrete
energy levels.

The Bohr Model of the

atom

The Bohr Model of the

atom
Each energy level (orbit) may be occupied by an

electron of that particular energy.

When

an atom absorbs energy, an electron can jump to

a higher energy level, farther away from the nucleus.

The

excited atom can then emit EMR as the electron

falls back down to a lower energy level.

When

an electron moves from one energy level to

another; this is called an electronic transition.

The

emitted energy is seen as a line in the spectrum.

The

difference in energy; E = E(higher)

E(lower)

Recall

E=h, Therefore E=h

That

is, the frequency of the emitted

radiation depends on the energy level
difference (E)of that particular transition.

Electronic

transitions between energy

levels results in emissions of radiation of
different frequencies and therefore
produce different lines in the spectrum.

Bohr

labelled each of the energy levels with a

number called the principal quantum
number, n.

The

energy level closest to the nucleus is

labelled n=1, the next n=2 etc.

Each
The

of these energy levels is called a shell.

principal quantum number defines the

energy level of the electron in a given shell.

Summary of The Bohr Model

An electron moving in an orbit have only certain
amounts of energy.
The energy the electron needs to move around in
an orbit is dependent on the radius of the orbit.
If the energy of an electron is quantised then the
radius of the orbit must also be quantised.
An electron moving in an orbit does not emit
energy. For an electron to move to another orbit it
must absorb energy to do work against the
attraction of the nucleus.
If an atom absorbs a photon (a quantum of
energy) it can promote an electron from an inner
orbit to an outer orbit.

The Balmer-Rydberg
Equation.
All

the lines in an atoms line spectra can be

determined by applying a relatively simple
formula.
1

1
1
2
2
nf
ni

Where nf and ni are quantum numbers of the

orbitals (integers)
ni> nf:
ni is energy level electron is leaving from
nf is energy level electron is going to
R = Rydbergs constant = 1.0977 10 -2 nm-1

Line Spectra of Hydrogen

For

hydrogen, a spectrum of four lines

is produced at 656.3 nm (red), 481.6
nm (blue-green), 434.0 nm (blue)
and 410.1 nm (indigo).

These

lines are known as the Balmer

Series (visible region).
The red spectral line results when n
= 3.

Line Spectra of Hydrogen

Hydrogen

also has lines that

extend into the non-visible
regions.
Spectral lines for hydrogen in the
ultraviolet region are known as
the Lyman Series
Lines in the infrared region
include the Pashen Series.

Energy Transitions within a Hydrogen

Atom
The

Lyman series
occurs when an
electron moves to
the nf=1 orbit from
any other orbit.

The

Balmer Series to
nf=2 from n= 3, 4
etc

The

Paschen Series
to nf=3 from n=4, 5
etc.

Summary of Electronic
Transitions
Series of Electron
Lines
Goes to:

Leaves
from:

Lyman

2, 3, 4 etc

Balmer
Paschen

2
3

3, 4, 5 ect
4, 5, 6 etc

Within

a
particular series:
The transition of
highest energy
has the highest
frequency and the
shortest
wavelength
hc

Recall
E=h =

Question
1.

What is the longest

wavelength line (nm) in the
Lyman series of the hydrogen
spectrum?
(Ans.= 121.5 nm)

2.

What is the shortest

wavelength (nm) in the Lyman
1
1
1

series of the
hydrogen
spectrum?
R

n
n
(Ans.= 91.2 nm)
2
f

2
i

R = Rydbergs constant = 1.0977 10-2 nm-1

Answers
1.

1 1
1
R 2 2
n

f ni
longest wavelength, lowest energy, i.e. between n f 1 and n i 2
1
1
1 1

R 2 2 1.097 10 2 nm 1 1 8.228 10 3 nm 1

4
1 2

(121.5nm)
The negative sign
8.228 10 3 nm 1

indicates that energy

was emitted

2.

1 1
1
R 2 2
n

f ni
shortest wavelength, highest energy, i.e. when n is infinetely large. Therefore n f 1 and n i
1
1 1
R 2 2 1.097 10 2 nm 1 1 0 (1.097 10 2 nm 1 )

1
1

91.2nm
1.097 10 2 nm 1

Summary
An

atom can only absorb or emit certain

amounts of energy..hence each atom has
a different emission/absorption spectrum.
Energy levels within an atom are quantised.
Evidence of the quantisation of energy acquired
from information on the photoelectric effect.
Energy

dependent on frequency and not

intensity.
Electromagnetic waves sometimes behave
like particles.

Quantum Mechanics The Heisenberg

Uncertainty Principle.
This

abandons the notion of an electron as a

small particle that moves in a specific path
around the nucleus. It focuses on the wavelike
properties of the electron.
To determine the position of the electron light
photons would have to interact with the
electron.
Such an interaction would increase the energy
of the electron causing it to move faster.
Difficult to determine a position that is constantly
changing

The Heisenberg Uncertainty

Principle.
It

is impossible to determine both the

position and the momentum of an
electron in an atom simultaneously
with great certainty.

Wave functions and Quantum

numbers
Heisenberg

showed an electrons position can never

be accurately be determined.
A wave function, however, tells where the electron
will most probably be found.
Schrdinger Wave Equation.
Wave function, : describes e- in atoms
2: gives the likely location of e- at an instant in
time.
The area the electron is located is called an orbitals
(spatial distribution of electron density)
Probability of finding an electron in a region of space (2)

Orbitals are defined by Quantum numbers: n, l, ml

Wave Equation Wave function or Orbital Probability of finding the electron 2

(n) Principal Quantum

Number
Relates

to the average distance of the e -s from the

nucleus.
This was called shell in CSEC.
This is a positive integer (n = 1,2,3)
It

determines the size and energy level of the orbital

As

n increases the number of allowed orbitals

increase and the size of the orbitals become larger,
This allows for electrons to be located far from the
nucleus

As

n increases the energy of the electron in the

orbital also increases

(n) Principal Quantum

Number
According

to n, orbitals are grouped

into layers called shells around the
nucleus
The number of electrons a shell can
hold is equal to 2n2. Where n is the
principal quantum number.
First shell (energy level): 2(1)2 = 2
Second shell: 2(2)2 = 8
Third shell: 2(3)2 = 18
Etc.

Each orbital can hold two electrons.

Orbitals are denoted s, p, d and f.
At each energy level the possible
number of orbitals are:
s1
p3
d-5

A shell is therefore a group of

orbitals with same principal quantum
number.
A sub-shell is a set of similar
orbitals of the same principal

The Angular-momentum
Quantum Number (l)
This

defines the three dimensional shape of the

orbital in which the electron moves.

The

number of possible shapes is related to the

principal quantum number.

When

the principal quantum number is n, the

angular-momentum quantum number has values
from 0 to n-1.
n= 1, then l = 0
n= 2, then l = 0 or 1 etc.

Quantum number
(l)

Sub-shell notation

The Magnetic Quantum Number

(ml)
This

defines the spatial

orientation of the orbital along a
standard set of coordinate axes

When

the angular-momentum
quantum number is l, the
magnetic quantum number has
values from l to +l

Magnetic Spin Quantum

Number (ms)
That

property of an electron which gives rise to its angular

momentum about an axis within the electron.

It

can be thought of as being right-handed or left-handed,

clockwise or counter clockwise: Electron spin

It

can have either of two values: m s = + or

The

magnetic spin quantum number of an electron is independent

of the first three quantum numbers that defines the orbital.

ms

refers to energy: both values are the same energy; however, it

is lower if electrons are not paired and spinning in the same
direction

Quantum Numbers

Quantum Numbers
Symbol

Values

n (principal)

Description

1, 2, 3, ..

Orbital size and

energy

l (angular)

0, 1, 2, .. n-1
Orbital shape or
type (sub-shell)

ml (magnetic)

-l..0..+l

Orbital orientation
in space

Total # of orbitals in lth subshell = 2 l + 1

n
l
ml

1
0
0

2
0
0

2
1
-1

name

1s 2s 2p

2
1
0

2
1
+1

3
0
0

3
1
-1

3
1
0

3
1
+1

3
2
-2

3
2
-1

3
2
0

3
2
+1

3
2
+2

2p

2p

3s

3p

3p

3p

3d

3d

3d

3d

3d

Question

Give the possible combinations of

quantum numbers for the following
orbitals:
(a) 3s
(b) 2p
(c) 4d

Solution
a.

n = 3, l = 0, ml = 0

b.

n= 2, l = 1, ml = -1, 0, 1

c.

n = 4, l = 2, ml = -2, -1, 0, 1, 2

Shapes of Orbitals s
Orbital
These

are spherical

There

is only one possible orientation

of a sphere: ml = 0

There

is one s orbital per shell

The

size on the orbital increases as

you go to a higher shell

Beyond

the first shell, there are several

regions of maximum probability

Shapes of Orbitals p
These are dumbbell-shaped.
Orbital

The

electrons are distributed in identical lobes on either side of the nucleus.

The

lobes are separated by a nodal plane that cuts through the nucleus.

When

l = 1, ml has three possibilities, one along the x, y and z axes oriented

at 900 angle to each other.

As

n increases, the size of the p orbital increases

Multi-electron Atoms
For

hydrogen, the energy of an orbital is determined by n

For

multi-electron atom, the energy level of the orbitals depend

on the shell as well as the sub-shells

Within

a given shell, the orbitals have slightly different

energies

This
As

is due to electron-electron repulsion

a result, outer shell electrons are shielded from the effects of

the nucleus by the inner shell electrons

Electron Configurations (E.C.)

Electron

Configurations refers to the

arrangement of electrons in an atom

Each

atom has its own electronic

configuration

There

are 3 basic rules to writing

electron configurations.

Rules to follow for writing

Paulis Exclusion Principle
E.C.

No 2 e- in an atom can have the same set of

quantum numbers.
Therefore, no atomic orbital can contain more
than 2 e- and they must spin in opposite
directions.
Aufbaus Principle
An electron occupies the lowest energy orbital that
can accommodate it.
Hunds Rule
Orbitals of equal energy are each occupied by one ebefore any orbital is occupied by a second e-, and all
e- in singly occupied orbitals must have the same spin

Electronic configuration
General notation:
1s2
Number of
electrons in orbital

Principal quantum
number

orbital

Energies of Orbitals

For a oneelectron
hydrogen
atom, orbitals
on the same
energy level
have the same
energy.

That is, they

Energies of Orbitals

As the number of
electrons increases,
though, so does the
repulsion between
them.

Therefore, in manyelectron atoms,

orbitals on the
same energy level
are no longer
degenerate

Energies of Orbitals
START HERE AND MOVE
ALONG THE ARROWS ONE
AT A TIME

Electronic Configuration
Based

on the representation the

atomic number of aluminum is 13
27
13

Al

What

is its E.C?
1s2 2s2 2p6 3s2 3p1
[Ne] 3s2 3p1

 There is an overlap of the

third and fourth shell of an
atom. As a result the 4s
orbital is of lower energy
(closer to the nucleus) than
the 3d orbital. Therefore the
4s orbital is filled first
(Aufbau principle).
When the 4s orbital is full,
there is some repulsion by
the inner electrons and the
4s pushed further away
from the nucleus. As a result

 In the formation of ions,

atoms lose electrons from the
orbitals of highest energy,
therefore the 4s electrons are
lost first.

Electronic configuration of
ions
E.C.
To

for Fe in FeCl3

solve:

Need to determine the oxidation number of Fe

in FeCl3

Recall:

The oxidation state of an uncombined

element is zero.
The sum of the oxidation states of all the
atoms or ions in a neutral compound is
zero.

Element

Usual oxidation
state

Exceptions

Group 1 metals

always +1

Group 2 metals

always +2

Oxygen

usually -2

except in peroxides
and F2O

Hydrogen

usually +1

except in metal
hydrides where it is
-1

Fluorine

always -1

Chlorine

usually -1

except in compounds
with O or F

Sulphate ion

(SO4)2-

Carbonate ion

(CO3)2-

Electronic Configuartion
FeCl3
Chlorine

is -1.

is in group 7, therefore oxidation number

Fe x Cl 31 0
i.e.

x ( 3) 0
x 3

Therefore

find the E.C. of the Fe3+ ion.

First find E.C. of Fe
Atomic # = 26
E.C. for Fe = 1s2. 2s2 2p6.3s2 3p64s23d6
Transition

elements lose electrons from the 4s

orbital before the 3d.

Electronic Configuration
E.C.
This

for Cr in CrCl3

is a neutral compound so the sum of the

oxidation states is zero.
Chlorine has an oxidation state of -1. If the
oxidation state of chromium is n:
n + 3(-1) = 0
n = +3
Therefore Cr in CrCl3 is actually the Cr3+ ion.

Electronic Configuration
52
24

Cr

p 24
e 24
Expected E.C. 1s 2 . 2s 2 2p 6 .3s 2 3p 6 .4s 2 3d 4
Actual 1s 2 . 2s 2 2p 6 .3s 2 3p 6 .4s1 3d 5
52
24

Cr 3

p 24
e 21
1s 2 . 2s 2 2p 6 .3s 2 3p 6 .3d 3 [ Ar ]3d 3

Orbital Filling Diagrams

These

diagrams are based on the electron

configuration.

In

orbital diagrams:

Each orbital (the space in an atom that will hold a

pair of electrons) is shown.
The opposite spins of the electron pair is indicated.

Orbital Diagram Rules

Represent each electron by an arrow
The direction of the arrow represents the electron spin
Draw an up arrow to show the first electron in each
orbital.

Hunds Rule: Distribute the electrons among the orbitals

within sublevels so as to give the most unshared pairs.
Put one electron in each orbital of a sublevel before the
second electron appears.
Half filled sublevels are more stable than partially full
sublevels.

Orbital Diagram Examples

H

_
1s

Li

_
1s

__ __
1s

2s

2s

2p

_
1s

2s

2p

Orbital Filling

Question
Give

the ground state electron configuration of

arsenic (Z = 33). Draw orbital filling diagram,
indicating the electron as up or down.