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ATOMIC

STRUCTURE
Chemistry @ MBCC
Pre-University Sciences
Science 1

1.1 Discuss the process of


theoretical change with respect
to Daltons atomic theory

Hypothesis
What is a hypothesis?
An educated guess, based on observation
A hypothesis can be used to:

to guide experimentation
aid in problem solving
help develop new theories
Hypotheses
can be supported or refuted through experimentation
can be disproven, but not proven to be true

Theory
Scientific theory summarizes a hypothesis or group
of hypotheses that have been supported with repeated
testing
Theories are well-established explanations for
experimental data
A theory is an accepted hypothesis
Theory
valid as long as there is no evidence to dispute it
usually can not be proven, but can be disproven

DALTONS ATOMIC
THEORY
Four main assumptions:
1. Matter consists of small particles called atoms
2. Atoms are indestructible or indivisible
3. Atoms of the same elements are identical in mass &
properties
4. Atoms combine chemically in simple whole number
ratio to form compounds
- Atoms combine in more than one simple whole number ratio

DALTON ATOMIC THEORY


TWO errors in Daltons Theory:
1. Atoms are indestructible or indivisible

Atoms can be sub-divided into subatomic


particles (Protons, Electrons, Neutrons)

Atoms can be destroyed by nuclear reactions


(splitting of the nucleus)

Amendment Atoms cannot be created,


destroyed, or transformed into other atoms
in a chemical change

DALTON ATOMIC THEORY


TWO errors in Daltons Theory:
2. Atoms of the same elements are
identical in mass & properties

Isotopes of atoms exists which have different


properties

Isotopes have different masses

Amendment Elements are characterized


by the nuclear charge of their atoms

Daltons Notebook
A page from Dalton's

notebook, burned
in the bombing of
Manchester
in World War II
Note the

incorrect formula for


water (OH)

1.2 Describe the structure of the


atom

Atomic Structure
Atoms are electrically neutral species
Contains equal numbers of Protons and Electrons
Neutrons are uncharged
Nucleus

Contains protons and neutrons


Held by powerful nuclear forces
Electrons
Orbit the nucleus
HomeWork
Read and make notes on Discovery of Subatomic
Particles (Chapter 1, pg 3-4)

Subatomic Particles
Mass of subatomic particles is measured

relative to one twelfth of the mass of a carbon12 isotope


Charge is relative to proton and electron
Particles

Relative Mass

Relative
Charge

Location

Proton

+1

Nucleus

Neutron

Nucleus

Electron

1/1837

Orbital

Electrons
(lightest) are
deflected at large
angles to the
positive (+) poles

Protons
(heaviest) are
deflected at
smaller angles
towards the
negative () poles

Neutrons
(uncharged)
continue
undeflected
through the field

Behaviour of subatomic
particles in an Electric (or
Magnetic) field

Use Flemings

left hand rule


the Xes in the

diagram
represent
magnetic field
going into the
paper
Lighter

particles are
deflected
more
compared to
the heavier
particles

Behaviour of particles in
a Magnetic field

http://term2chemace.wikispaces.com/1.2+-+Behaviour+in+Different+Types+of+Fields

1.3 Define the following


terms:
M A SS N U M B E R
ISOTOPES
R E L AT I V E I S O T O P I C M A S S ( R I M )
R E L AT I V E AT O M I C M A S S ( R A M )

Review: Definitions
Atomic Number (Proton number)
Number of protons in the nucleus of an atom
Mass Number (Atomic Mass/Nucleon Number)
sum of the protons and neutrons in the nucleus of the atoms

Relative Isotopic Mass


the ratio of the mass of one atom of that isotope to one
twelfth of the mass of one atom of carbon-12 isotope

Relative Atomic Mass


the ratio of the average mass of one atom of an element to
one twelfth of the mass of an atom of carbon-12 isotope

Isotopes
Atoms of an element that have the same

atomic number but different mass numbers

Same number of protons but different


number of neutrons

Identical chemical properties (same


number of electrons)

Different physical properties (different


masses)

Isotopes
Element

Hydrogen

Carbon
Chlorine
Bromine

Isotope

Atomic
Number
(Protons)

Neutrons

Mass
Number

Hydrogen-1

Hydrogen-2

Hydrogen-3

Carbon-12

12

Carbon-13

13

Chlorine-35

17

18

35

Chlorine-37

17

20

37

Bromine-79

35

44

79

Bromine-81

35

46

81

Relative Isotopic Abundance


The relative abundance of each isotope in a given
element is the ratio or percentages in which
they exist in the world

Relative isotopic abundances are used to calculate


the Relative Atomic Mass of elements in the
periodic table

The mass of an element depends on the


relative abundance of its isotopes

Relative Atomic Mass: Calculations


Calculate the relative atomic mass (Ar) of chlorine
from the mass spectrum data of chlorine atoms
given below.
Atomic
Atomic
Relative abundance
Isotope
Weight
(%)
35

Cl

34.97

75.8

37

Cl

36.97

24.2

Relative Abundance: Calculations

75.8
24.2

Ar
34.97
36.97
100
100

A r 26.507 8.947
A r 35.45

Relative Abundance: Calculations


Calculate the relative isotopic abundance of
the two isotopes of chlorine (35Cl and 37Cl)
given the following data below.
Atomic
Isotope

Atomic
Weight

Natural Cl

35.45

35

Cl

34.97

37

Cl

36.97

Relative Abundance: Calculations


x = fraction 37Cl
1 x = fraction 35Cl
36.97( x ) 34.97(1 x ) 35.45
36.97 x 34.97 34.97 x 35.45
2.00 x 0.48
x 0.24 ~ 24%
1 x 0.76 ~ 76%

Homework
Calculate the relative atomic mass (Ar) of
zirconium from the mass spectrum data of zirconium
atoms given below.

Atomic
Isotope

Atomic Weight

Relative Abundance/%

Zr

90

51.5

Zr

91

11.2

Zr

92

17.1

Zr

94

17.4

Zr

96

2.8

90
91
92
94
96

Home Work
Calculate the relative isotopic abundance
of the two isotopes of hydrogen (1H and 2H)
given the following data below.
Atomic Isotope Atomic Weight
Natural H

1.0080

1.0078

2.0141

Radioactivity
1.4 E xp la in th e ph en o menon
of ra di oa cti v ity

Radioactive Isotopes
Nucleus
Strong nuclear force of attraction between nucleons
(protons & neutrons)

As number of protons increase the positive charges


in the nucleus repel each other

Number of neutrons increase more rapidly than the


number of protons in order to try & stabilize the
nucleus

Nuclei with >84 protons are unstable

Nuclei Stability
Nuclei becomes stable by impulsively ejecting
radioactive particles or radiation
Alpha particles
Beta particles

4
2

He 2

0
1

Gamma radiation

Emission of alpha & beta particles changes the


number of protons in the nucleus
Different atom is produced

Behaviour of Radioactive Particles


in an Electric Field

Behaviour of Radioactive
Particles in a Magnetic Field

Alpha Particles

2
He
Helium Nuclei

Emission leads to decrease in atomic number by 2 and


mass number by 4

4
2

4
2

Symbol

He

238
92

is used in nuclear reactions

U He
4
2

234
90

Th

Beta Particles

Neutron disintegrates to a proton and an electron


1
0

n 11p

0
1

Proton remains in the nucleus; beta particle is emitted


from nucleus

Atomic number increases by 1; Mass number


unchanged
24
11

Na

0
1

24
12

Mg

Gamma Radiation
Electromagnetic waves of short wavelength
Emission of alpha or beta particles are usually
accompanied by emission of gamma rays

Emission of particles (alpha or beta) results in


atomic nucleus being excited; excess energy
is released as gamma rays and nucleus
returns to a more stable energy level

Radioactivity Band of Stability

Repulsion between the positive charges of protons


is minimized by the presence of neutrons

As atomic number increases, the neutron to


proton (n/p) ratio must also increase to keep
the nucleus together

In large atoms, increasing the number of


neutrons is not enough to keep the nucleus
together, therefore, nucleus becomes unstable
(radioactive)

Band of Stability
Plot of

the number of Neutrons vs number


of Protons in a stable nuclei

Stable nuclei are located in a shaded area


of the graph

Shaded area is known as the Band of


Stability

Radioactive nuclei occur outside this band

Nuclei above
the band of
stability with a
high n/p ratio
can move
towards the
band of stability
by emitting a
beta particle

Heavy nuclei
with atomic
number >84
tend to move
towards stability
by emitting an
alpha particle

Band of Stability

1.5 Cite the use of


radioisotopes

http://ccef-coree.com/wp-content/uploads/2010/05/image033.jpg

Homework
1. Find seven or more uses of radioactive isotopes?
2. Find six ways in which radioactive waste is
disposed?
3. List and explain the main steps involved in Mass
Spectrometry
4. Draw and label a diagram of a Mass Spectrometer
5. List the uses of Mass Spectroscopy

1.6 Calculate the RAM of mass of an


element, given isotopic masses and
abundances

Mass
Spectrometer is
used to analyze
the masses of
isotopes and
their relative
abundances
Principle of MS
1. VAPOURISATIO
N
2. IONISATION
3. ACCELERATION
4. DEFLECTION
5. DETECTION

The Mass
Spectrometer

Principles of Mass Spectrometry


Vapourisation

Sample is injected; heat is supplied to convert into gaseous form


X(l) X(g)
Ionisation

Gaseous sample bombarded with high energy electrons; cation is formed


X(g) + e- X+(g) + e- + eAcceleration

Ions are accelerated through an electric field and towards a magnetic


field
Deflection

Fast moving ions are deflected by magnets; lighter ions are deflected the most
Angle of deflection depends on m/z ratio
Detection

Detector records each species as a peak on a chromatogram

Percentage
abundance (or
intensity) vs
m/z
m/z is mass to
charge ratio
Ions with a
single charge
are selectively
accelerated
Ions with a
single charge
have m/z value
which is
equivalent to
mass itself

Mass

Homework
Use the data from the mass spectrum below to
determine the RAM of the element

1.7 Explain how data from emission


spectra provide evidence for discrete
energy levels within an atom

White light when


focused through
a prism,
disperses into
different
components and
produces a
continuous
spectrum
Visible light is
just one type
ofelectromagn
etic radiation

The Electromagnetic

EMR Wave-particle duality


Electromagnetic radiation (EMR) is a form of

transmitted energy
EMR consists of all types of energy that can be
seen, felt or recorded
EMR can be viewed as:

Particle
Wave

EMR Particle
EMR can be viewed as particles (packets) of

energy, called photons or quanta travelling


in a wave-like pattern at the speed of light
Photons

Have no mass
Travel in wavelike pattern
Speed of light (High Velocity)

EMR Wave
EMR can be viewed as a travelling wave

EMR Wave (Contd)


Waves are characterized by:

Wavelength
Frequency
Velocity (Speed)

EMR Wave Definitions


Wavelength () distance between successive

crests or successive troughs of a wave


Frequency () number of waves (cycles or

oscillations) that pass a given point in space in


one second (Hertz)
Speed of light (c) speed of EMR in a vacuum

All EMR travel at the speed of light, c = 3 x 10 8


ms-1

EMR Plancks Equation


Energy of a photon is directly proportional to
the frequency of the radiation

E h
where: E is the energy (J)
h is Plancks constant (6.63 x 10-34 J s)
is frequency (Hz or s-1)

EMR Calculations
The wavelength and frequency of EMR are
related
c

c = 3 x 108 ms-1

Useful Conversions

1 m = 100 cm = 1 x 106 m = 1 x 109 nm


1 nm = 1 x 10-3 m = 1 x 10-7 cm = 1 x 10-9 m

EMR Calculations
Energy can be expressed in terms of the speed of
light, wavelength or wavenumber

hc
E h

c is the speed of light (c = 3 x 108 ms-1)


is the wavelength
Energy is inversely proportional to the
wavelength

Relationship between Energy, Frequency and


Wavelength

Electromagnetic Radiation: Calculations

Calculate the energy of a photon with a


wavelength of 5 m

1 m is equal to 10-6 m
5 m is equal to 5 x 1 x 10-6 m = 5 x 10-6 m

hc 6.63 x 10-34 J s x 3 x 108 m s-1


E

5 x 10-6 m
E 3.978 x 10-20 J

Useful Conversions
Deci, d 10-1
Centi, c

10-2

Milli, m

10-3

Micro , 10-6
Nano, n

10-9

Pico, p 10-12
Femto, f

10-15

Atomic Spectra
Atoms interact with EMR
Atoms absorb (or emit) light of a
particular wavelength (or frequency)

The pattern of frequencies absorbed


by the atom produces a
discontinuous pattern or spectrum
(absorption spectrum)

Hydrogen Absorption Spectrum

Atoms heated to high enough temps


emit light of a certain wavelength;
produces an emission pattern
(emission spectrum)

Atomic spectra provide evidence for


the arrangement of electrons in the
atom

Hydrogen Emission Spectrum

Continuous vs. Discontinuous


Spectrum
Continuous Spectrum

No distinct division between the colours


Discontinous (Line) Spectrum

Distinct lines
Two types of line spectrum
Absorption spectrum
Emission spectrum

Absorption Spectrum
A Line spectrum

Dark lines represent the wavelengths of light


absorbed by element

Unique spectrum produced

Emission Spectrum
A Line spectrum
Coloured lines on dark background represent
wavelengths of light emitted by element

Unique spectrum produced

Hydrogen Emission Spectrum

Energy Levels
Atoms and molecules have
unique set of energy levels

Electrons in an atom can exist


only in discrete energy levels

Lowest energy level is the ground


state
Higher energy levels are excited
states

Absorption & Emission


Absorption
Quantum of energy (photon) is supplied to an atom &
is absorbed by electrons in the ground state

The electron moves to a higher energy level (excited


state)

Emission
Quantum of energy (photon) is emitted from the atom
resulting from the excited electron in a higher energy
level falling back to a lower energy level

Absorption & Emission

Absorption & Emission

Atomic Spectra
Each element produces a unique spectrum that
can be used to identify it

Why are discrete lines seen in


atomic spectra?
Bohrs model of the atom

explains
Energy of the electron is

quantised
Atom or molecule absorbs or

emits a quantum of energy


exactly equal between two
energy levels
E = E1 E0
The greater the difference in

the energy levels, the higher


the frequency of light emitted

Emission Spectrum of
Hydrogen
Each line in the emission (line) spectrum of
hydrogen

Specific frequency
Specific wavelength
Specific quantum of energy (E = Ey Ex)
Evidence: Discrete energy levels in the atom

Energy Levels & Quantum Numbers


Energy levels of an electron within an atom are
assigned the letter n.
n = PRINCIPAL QUANTUM NUMBER
Lowest energy level (Ground state) closest to
the nucleus, n = 1
Next highest energy level , n = 2 and so on

Each line in the


emission spectrum
of hydrogen arise
from a particular
transition of the
electron from an
orbit of higher
energy level to an
orbit of a lower
energy level

There is a point in
spectrum where the
lines converge

Convergence
corresponds to
electrons falling
from the highest
possible energy
level (highest
frequency)

Origin of Lines in Emission


Spectrum

Line Series

Line Series in Emission Spectrum


Lyman series
Electron transitions from higher energy levels to principal
quantum number, n = 1

Balmer Series
Electron transitions from higher energy levels to principal
quantum number, n = 2

Paschen Series
Electron transitions from higher energy levels to principal
quantum number, n = 3

Line Series in Emission Spectrum


Brackett Series
Electron transitions from higher energy levels to principal
quantum number, n = 4

Pfund Series
Electron transitions from higher energy levels to principal
quantum number, n = 5

In each series, the lines comes closer together


as the frequency increases together until it
converges to from a continuous spectrum

1.8 Describe the atomic


orbitals

Schroedinger Wave Equation


Wave-particle duality of electrons
The position of an electron is described in terms of
probability density

An orbital is a region (volume of space around the


nucleus) where there is a high probability of finding
an electron of a given energy (95%)

Schroedinger Atomic model


3-D
3 quantum numbers (principal, angular, magnetic)

Quantum numbers
The properties of an atom's electron
configuration are described by four quantum
numbers

Quantum numbers describe the:


size
shape
orientation in space of the orbitals of the electron

First Quantum Number


Principal Quantum Number (n)
Energy

levels are assigned the letter n


Maximum number of electrons at n level is
2
2nEnergy
Level
No. of electrons
n
n
n
n

=
=
=
=

1
2
3
4

2
8
18
32

Second Quantum Number


Angular Quantum Number (l)
Sublevels

in n & Shape of the orbitals

s,

p, d, f
Each energy level has n sublevels
Energy
Level
n=1
n=2
n=3
n=4

No. of
Sublevels
1
2
3
4

Sublevels
1s
2s, 2p
3s, 3p, 3d
4s, 4p, 4d,
4f

Shapes of Orbitals

Shapes of Orbitals

Third Quantum Number


Magnetic Quantum Number (m)
Number

of orbitals within a sublevel

Sublevel
s

No. of
Orbitals
1

Max.
Electrons
2

10

14

Fourth Quantum Number


Spin Quantum Number (ms)
Each electron has a magnetic field and a spin
associated with that electron
Pauli Exclusion Principle
No more than two (2) electrons can occupy an orbital
Two (2) electrons in the same orbital must have opposite
spins
NO TWO ELECTRONS IN AN ATOM HAVE THE SAME
FOUR QUANTUM NUMBERS

Quantum Numbers

1.9 Describe the shapes of the s


and p orbitals
S O R B I TA L
P O R B I TA L

s Orbitals

Spherical
Each energy level has one s orbital
Maximum number of electrons = 2
1s and 2s orbitals are similar in shape however
electron density is closer to the nucleus for the 1s
orbital

p Orbitals
Dumb-bell shape
Each energy level has three (3) degenerate p
orbitals i.e. three (3) orbitals of EQUAL ENERGY

1.10 Determine the electronic


configurations of atoms and ions in
terms of s, p and d orbitals
AU F B AU PR IN C I PL E
PA U L I E X C L U S I O N P R I N C I P L E
HUNDS RULE

Electronic
Configurations
How do we fill up energy levels with electrons?
We use three rules

1. Aufbau Principle
Electrons are added one at a time,
starting with the lowest energy orbital
s orbitals have slightly lower energy than the p
orbitals in the same energy level i.e. 2s < 2p

s orbitals will ALWAYS fill before corresponding p


orbitals

s orbital have the lowest energy compared to p, d,


and f

s<p<d<f

1. Aufbau Principle
(Contd)
Anomaly
Irregularity in the position of the 3d and 4s orbitals
3d has slightly more energy than 4s
4s fills first then 3d orbitals followed by 4p orbitals

2. Pauli Exclusion
Principle
No more than two electrons can occupy an orbital
The two (2) electrons in the same orbital must
have opposite spins

Why?

3. Hunds Rule

Electrons fill degenerate orbitals


one at a time with parallel spin
before a second electron is added
with opposite spin

Electronic Configurations (E.C)


Can you use these rules to fill up the
energy levels for the first twenty
elements?
Three methods can be used to write the E.C:

1. Electron in the box method


2. Orbital method
3. Shortcut orbital method

Electron-in-Box Method
The E.C for nitrogen may be written as:

Write the configuration for:


Carbon
Oxygen
Phosphorus
Calcium

Orbital Method
Principal Quantum number (1, 2, 3 etc.)
Symbol for the orbital (s, p, d, f)
Superscript that shows the number of electrons in
the sublevel

Orbital Method and Shortcut


Method
For potassium, the
arrangement of
electrons is:

We can use the

Orbital method to
write the E.C as:
But remember the

nearest noble gas to K


has an E.C of:
We can use a shortcut

method to write the


E.C:

Electronic Configurations Abbreviated

He, Ne and Ar have electronic


configurations with filled shells of orbitals
Abbreviated electronic configurations for noble
gases
He = 1s2 or [He]
Ne = 1s2 2s2 2p6 or [Ne]
Ar = 1s2 2s2 2p6 3s2 3p6 or [Ar]

Electronic Configurations
Atomic Number

Symbol

Electronic
Configuration

1s1

He

1s2 or [He]

Li

[He] 2s1

Be

[He] 2s2

[He] 2s2 2p1

[He] 2s2 2p2

[He] 2s2 2p3

[He] 2s2 2p4

10

Ne

[He] 2s2 2p5


[He] 2s2 2p6 or
[Ne]

Electronic Configurations
Atomic Number

Symbol

Electronic
Configuration

11

Na

[Ne] 3s1

12

Mg

[Ne] 3s2

13

Al

[Ne] 3s2 3p1

14

Si

[Ne] 3s2 3p2

15

[Ne] 3s2 3p3

16

[Ne] 3s2 3p4

17

Cl

[Ne] 3s2 3p5

18

Ar

[Ne] 3s2 3p6 or [Ar]

19

[Ar] 4s1

20

Ca

[Ar] 4s2

Electronic Configurations
Atomic Number

Symbol

Electronic
Configuration

21

Sc

[Ar] 4s2 3d1

22

Ti

[Ar] 4s2 3d2

23

[Ar] 4s2 3d3

24

Cr

[Ar] 4s1 3d5

25

Mn

[Ar] 4s2 3d5

26

Fe

[Ar] 4s2 3d6

27

Co

[Ar] 4s2 3d7

28

Ni

[Ar] 4s2 3d8

29

Cu

[Ar] 4s1 3d10

30

Zn

[Ar] 4s2 3d10

Electronic Configurations Anomaly


After 3p orbitals are filled, 4s orbital is filled
before the 3d orbital

4s orbital is at a slightly lower energy than


the 3d
K is [Ar] 4s1
Ca is [Ar] 4s2
Sc is [Ar] 4s2 3d1

Filling up Orbitals

Electronic Configurations Anomaly


At Sc, the 3d orbitals begin to fill up (recall
Hunds rule)
Irregularity is seen in the electronic
configuration of Cr and Cu

Cr is [Ar] 4s1 3d5

Cu is [Ar] 4s1 3d10

E.C The Case of Cr and


Cu
A subshell is particularly stable if it is half full

or full
Given two configurations, the atom would
"choose" the more stable one
For example:
Cr

has an E.C of [Ar]4s13d5 instead of


[Ar]4s23d4

Cu

has an E.C of [Ar]4s13d10 instead of


[Ar]4s23d9

An s electron can jump into the d orbital, giving

Electronic Configurations Anomaly

Half-filled and filled sublevels of 3d orbitals

decreases energy
Spin pairing of the 4s orbital increases energy

https://www.caymanchem.com/app/template/chemAssistant,Tool.vm/itemid/4001

Electron Configurations of Ions


Q.Write the E.C of Al3+
Aluminum loses three electrons when it forms an ion.
The neutral atom of aluminum has 13 electrons
The ion of aluminum, Al 3+, has lost three electrons and
only has 10.
Thus, you should write the electron configuration for
Al3+ with 10 electrons Al3+: 1s22s22p6 or [Ne]

If the element is a cation (positive charge), you


mustsubtractelectrons from your total

If the element is ananion (negative charge), you


mustaddelectrons to your total

Electron Configurations of Ions (Contd)


Q.Write the E.C of Fe3+
The Fe atom has lost 3 electrons in this case
Fe has an E.C of [Ar] 4s2 3d6
Fe3+ has an E.C of [Ar] 3d5 because two electrons

are lost from 4s orbital and one electron is lost


from 3d orbital
Electrons are removed from the valence
shell4sorbitals before they are removed from
valence3dorbitals when transition metals are
ionized

1.11 State the factors which


influence the first ionisation
energy of elements

Ionization Energy (I.E)


1st Ionization Energy of an element
Energy needed to convert 1 mole of its gaseous
atoms into gaseous ions with a single positive
charge

Energy required to remove each successive


electron is called the 2nd, 3rd, 4th, etc. ionization
energy
Ionization energies are positive because it
requires energy to remove an electron

Factors Influencing I.E


The magnitude of I.E depends on how strongly
the electron (to be lost) is attracted to the nucleus

Three factors influence the I.E (how easily the


electron is lost):
1. Atomic Radii
2. Nuclear Charge
3. Shielding (Screening by inner electrons)

1. Atomic Radii
Atomic radiusis generally stated as being
the distance from an atoms nucleus to the
outermost orbital of electron

The I.E is influenced by the distance the


outer electron is from the nucleus

As distance increases:
nuclear attraction for the outer electron decreases
ionization energy decreases

Atomic radii (contd)


Successive Ionization Energies of Sodium (Na)
Ionization
Energy

Energy (kJ)

Orbital Electron Lost


From

1st

496

3s

2nd

4562

2p

3rd

6912

2p

4th

9543

2p

5th

13353

2p

6th

16610

2p

7th

20114

2p

2. Nuclear Charge
The effective nuclear charge (zeff )of an atom is
the net positive charge felt by the valence electron

As Zeff increases:
attraction of the nucleus for the outer electron
increases
ionization energy increases

Atomic radii and Electron shielding (screening of inner


e-) can outweigh the effect of nuclear charge

For eg. Cs has a larger nuclear charge than Na but a lower


first I.E (loses electron more readily) than Na
1st I.Ecaesium = 376 kJ/mol and 1st I.Esodium = 496 kJ/mol

3. Shielding (Screening by inner


electrons)
Electrons experience repulsion by other electrons
Outer electrons are shielded from the full attraction of
the nucleus by the repelling effect of inner electrons
(screening effect)
Screening effect of electrons in lower energy levels is
more effective than electrons in higher energy levels
Electrons in same energy level have negligible
screening effect on each other
As screening effect becomes more effective, ionization
energy decreases

Shielding (Screening by inner


electrons)

1.12 Explain how ionisation energy data provide


evidence for sub-shells
1.13 Derive the electronic configuration of an
element from data on successive ionisation
energies

Successive Ionization Energies


The energy involved in the removal of an electron

successively from an atom is called successive ionization


energy.
It relates to the next ionization energies after you have

removed the first electron (2 nd, 3rd, 4th IE etc.)


Unusually large increases in I. E occurs where all

electrons in the outer (valence) shell have been removed


and are now being removed from an inner shell
What do you expect to observe for the values of the
successive I.E in an atom?

Successive I.E for Selected


Elements

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Evidence of Energy levels (Shells)


Successive ionization energy increases because inner
electrons are attracted more strongly to positively
charged nucleus

Evidence of Energy levels (Shells)


Successive I.Es can be used to:

identify the group the atom is in by the number of


outer (valence) shell electrons
determine the number of electron shells in the atom

Successive I.E for Chlorine

Successive Ionization Energies Period 3

Element

1st

2nd

3rd

4th

Na

496

4562

6912

9543

101
2

1903

2912

4956

??

738

1451

7733

??

787

1577

3231

5th

6th

Group

13353 16610

2223
3

10540 13630 17995

??

4356

6273

16091 19784

??

Evidence of Energy Levels (Shells)


Successive Ionization Energies of Mg
5.0
4.5
log (IE) 4.0

Successive I.Es therefore

provide evidence for the


different energy levels

3.5

For example in Mg we

3.0

see that there are 3


energy levels

2.5

Evidence of Sub-energy levels (Orbitals)


Ionization energy increases across a period and decreases down
a group

I.E. Trends Across Period


Atomic radii decreases
Ionization energy increases

Anomalies
1st I.E. of boron is smaller than beryllium (similarly Al smaller than Mg)
1st I.E. of oxygen is smaller than nitrogen (similarly S smaller than P)

I.E. Anomaly ( B < Be)


Less energy is required to

remove the first electron from


the 2p orbital in B than from the
2s orbital in Be

2p electron is slightly more

distant from the nucleus than


the 2s

2p electron is partially screened

by the 2s electrons as well as the


inner electrons.

Both of these factors offset the

Be 1s22s2

effect of the extra proton in boron

1s2 2s22p1

I.E. Anomaly ( O < N)


It requires less energy to

remove a paired electron with


opposite spin

In nitrogen, the three electrons

in the 2p orbitals have the same


spin while in oxygen the fourth
2p electron is paired in one of
the orbitals (2px)

The electron-electron repulsion

of the two electrons in the same


orbital (2px2) means that the
electron would be easier to
remove, offsetting the effect of
the extra proton

N 1s2, 2s2, 2p3


O 1s2, 2s2, 2p4

Evidence of Sub-energy levels (Orbitals)

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