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Course Title: General and Inorganic

Chemistry
Course Code: FME 151/FBE 105/FCE 181
Lecturer and contacts
Mr. Vincent Madadi
Department of Chemistry, University of Nairobi
P. O. Box 30197-00100,
Nairobi, Kenya
Chemistry Dept. Rm 114
Tel: 4446138 ext 2185
Email: vmadadi@uonbi.ac.ke, madadivin2002@yahoo.com
Website: http://www.uonbi.ac.ke/staff/vmadadi
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Course content
1) Atomic structure:
Atomic structure & electromagnetic radiation,
Borhs atomic model & wave mechanical model of atomic
structure;
electron configuration & effective nuclear charge.
Periodic table & atomic properties
2) Chemical bonding:
ionic bond, covalent bond, metallic bond, hydrogen bond.
3) Chemical kinetics:
Rate of reactions and rate equations, factors that influence rate of
reaction, order of reaction, molecularity of reaction, activation
energy,

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Course content cont.

4) Chemical equilibrium:
Equilibrium law, Equilibrium constant, homogeneous
equilibrium, heterogeneous equilibrium, Lechateliers principle.
5) Solutions:
types of solutions, Henrys law, solubility and solubility curves,
solubility product, ionic equilibrium.
6) Adsorption:
types of adsorption, adsorption isotherms, application of
adsorption.
7) Environmental significance of some elements and salts:
Environmental segments, types of pollutants, air pollution, acid
rain, smog formation, green house effect, ozone layer, water
treatment.
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Examination
Two CATs = 15%
7 Practicals = 15%
Final Exam = 70%
Tutorial questions (Contribute to CAT marks)
CAT 1 (2nd November 2012)
CAT 2 (30th November 2012)
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1. ATOMIC STRUCTURE

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1.1 Composition of atom

Particle

Symbol Charge Charge (C)

Proton
Electron
Neutron
Name

Hydrogen

p+
eN

+
0

+1.6 10-19 C
-1.6 10-19 C
0

Symbol

Calculations

Helium

He
Neon

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Ne

Mass (Atomic
mass units)

Mass (kg)

1.673 x 10-27
9.108 x 10-31
1.675 10-27

1
1/1837
1

p = 1; n = 0; e = 1
A = p + n = 1+0 = 1;
Z=e=1
p = 2; n = 2; e = 2
A = p + n + 2+2 =4;
Z=e=2
p = 10; n = 10; e =10
A = p + n = 10+10 = 20
Z = e = 10

Representation of
subatomic particles in
elements
1

H
1
2

He
4
10

Ne
20

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http://periodictable.com/Posters/Poster3.2000.JPG

1.2 Spectroscopy
a) Definition:
Spectroscopy: The study of interaction of electromagnetic radiation
with matter.
Electromagnetic radiation: This is a stream of energy (called quanta
or photon) moving in the direction of propagation and perpendicular
to electric and magnetic field.
Characteristics of electromagnetic radiation (emr) : All forms of emr:
1) Do not require a medium to travel
2) Travel with velocity of light = 3 x 108 m/s
3) Have dual nature exhibit both wave and particle nature
4) It has electric and magnetic components oscillating in plane
perpendicular to each other and perpendicular to the direction
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8
of propagation.

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Characteristics of electromagnetic
radiation
Example of an electromagnetic wave with the magnetic field
oscillating parallel to the z-axis, the electric field oscillating
parallel to the y-axis, and the wave moving along the x-axis.
The x, y, and z-axes are perpendicular to each other.

Direction of propagation

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b) Properties of electromagnetic radiation

waves
1. Wavelength (symbol = pronounced as lambda): The
distance between two consecutive peaks in the wave.

1 m = 109 nm = 1010 = 1012 pm

nm = nanometre; = angstrom
pm = Pico-metre
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Properties of electromagnetic radiation

waves ...
2) Frequency ( symbol = , pronounced as nu): This is the
number of waves or cycles that pass a point on the x-axis
each second.
3) Velocity (symbol = c): All forms of electromagnetic radiation
travel at the speed of light, c = 3 x 108 m/s
Relationship between wavelength, frequency and velocity
These are related by the expression:

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C = ............................Eq. 1

= c/ and = c/ .....Eq. 2

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Properties of electromagnetic radiation

waves ...
Wave number ( symbol , pronounced as nu bar): This is the
reciprocal of the wavelength.

= 1/ = /c .............................Eq. 3
Examples:
Example 1. The limits of microwave region are approximately 1 GHz and 100
GHz, and those of the millimetre wave region are approximately 100 GHz and 300
GHz. Calculate the wavelengths associated with these frequencies .
Ans:
From equation 2, = c/

For

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1 GHz, = 3 x 108 m/s /1 x 109 s-1 = 0.3 m

100 GHz, = 3 x 108 m/s /100 x 109 s-1 = 3 mm
300 GHz, = 3 x 108 m/s /300 x 109 s-1 = 1 mm
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c) Calculating energy associated with

electromagnetic radiation- Plancks theory
of radiation.
1) Emission or absorption of energy does not take place
continuously but discontinuously in form of small packets or
bundles called quanta ( or photons in case of light).
A quantum is the smallest packet of energy wave that can exist
independently.
2) Each quantum is associated with a definite amount of energy
which is proportional to the frequency of radiation i.e.
E or
E = h ...........Eq. 4
Quantum or photon
Where h = Plancks constant = 6.626 x 10-34 Js

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13

Calculating energy associated with

electromagnetic radiation ...
3) The amount of energy emitted or absorbed by a body is in whole
number multiple of h (or quantum)

E = nh .........................Eq. 5
Where n = 1, 2, 3 etc but not 0.1, 0.8 etc.
This is called quantisation of energy implying that energy occurs
in whole number multiples of h
Example 2
Calculate the energy of one photon of radiation of:
a) Frequency 4.6 GHz
b) Wave numbers 37,000 cm-1
c) What is the energy of one mole of these photons?
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Calculating energy associated with

electromagnetic radiation ...
Ans:
a) E = hv = 6.626 x 10-34 Js x 4.6 x 109 s-1 = 3 x 10-24 J
1 mol = 6.022 x 1023 particles = Avogadros number of particles

For 1 mole of photons, E = NAhv = 6.022 x 1023 mol-1 x 3 x 10-24 J = 1.8 J
b) From equation 3, = 1/ = /c ; Hence E = hcv = 6.626 x 10-34 Js x 3 x 108
m/s x 37,000 x 102 m-1 = 7.3 x 10-19 J
For 1 mol, E = NAhv = NAhcv
= 6.022 x 1023 mol-1 x 7.3 x 10-19 J = 440,000 Jmol-1 = 440
kJmol-1
[Note: the other unit for energy is electron volt (eV).

1 eV = 1.60218 x 10-19 J = 96.485 kJmol-1

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d) Electromagnetic radiation spectrum

Definition: This is the entire range of electromagnetic
radiations separated into different wavelengths or frequencies.
Example:

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Spectrum
Definition: This is the separation or analysis of a composite
radiation into different wavelengths or frequencies .
Example: when white light is passed through a prism a
spectrum of seven colours (VIBGYOR) is obtained.

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Interaction of electromagnetic radiation

with matter /origin of spectrum
When an atom is bombarded by emr, it absorbs energy and
move to excited state with higher energy.
Two possible transitions occur giving rise to two different types
of spectra:
1) Absorption spectrum
2) Emission spectrum
i.e.
E1

E1

hv

hv
E0
Energy is absorbed, absorption spectrum
produced
E = E1 - E0 = hv

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E0
Energy is emitted, emission spectrum
produced
E = E1 - E0 = hv
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Interaction of electromagnetic radiation

with matter cont.

Intensity

The spectrum produced is characteristic for each element,

hence can be used to identify the element.
1) Emission spectrum:
Emission spectrum is produced by heating a substance directly
in a flame or electrically and passing the emitted radiation
through a prism or a grating.

Sample in
excited state

Grating

Spectrometer

Frequency

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Types of emission spectra

i) Continuous emission spectrum

It consists of a wide band of continuous wavelengths which
appear as continuous band of light.

It is produced by incandescent solids e.g. Hot filament , hot
iron etc.

The intensity of spectrum is not uniform over the entire
range i.e. is maximum at particular wavelengths

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Types of emission spectra cont.

ii) Line or atomic emission spectrum

It consists of discrete bright lines produced by gases or vapours
of a substance in atomic state.

The lines are regularly spaced but differ in their intensities.

Examples:
a) hydrogen line spectrum
b) sodium vapour spectrum
c) mercury vapour spectrum

Illustration:

Hydrogen line
spectrum

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21

Examples of atomic emission spectra of

elements

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22

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Types of emission spectra cont.

iii) Band emission spectrum

It consists of luminous bands separated by dark spaces.

It is produced by substances in molecular state.

At high resolution, each band is observed to be comprised of
very fine lines.

Examples: a) vacuum tubes
b) Carbon arc with metallic salt in its core
Luminous bands

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2) Absorption spectrum
Absorption spectrum is produced when light from a source
that emits a continuous range of wavelengths is passed
through a substance (solid, liquid or gas) at lower temperature
and observed through a spectrometer.

Source of
Continuous
radiation
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Intensity

The substance absorbs some of the wavelengths leaving dark

lines (or dark bands or continuous dark region) at their places.

Grating

Sample

Spectrometer

Frequency

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Types of absorption spectrum

Depending on the type of substance absorbing the radiation,
the spectrum can be:
i) Continuous absorption spectrum

Occurs when a continuous range of wavelengths are absorbed
by the sample producing continuous dark regions e.g. When
the glass absorbs all wavelengths except red
ii) Line absorption spectrum

It consists of discrete dark lines produced when absorbing
materials are in vapour or gaseous phase.

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Types of absorption spectrum

iii) Band absorption spectrum

It consists of dark bands produced in absorption spectrum of
aqueous solution e.g. KMnO4 gives five dark absorption
bands.

Difference between spectra

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1.3) Photoelectric effect

When a photon of light of sufficient frequency (v) and energy (hv)
strikes a metal surface, electrons are ejected.
Part of the photon energy is consumed to separate electrons from
the metal surface (threshold energy or hvo),
The remaining energy is imparted to eject electron to a certain
velocity (v), thus the emitted electron gains kinetic energy (KE or
mv2). This can be represented as:

hv
Photon energy
or incident energy

= hvo + mv2 .....................Eq. 6

Work function of
A metal

Kinetic energy of an
emitted electron

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Photoelectric effect ...

Where , h = Plancks constant = 6.626 x 10-34 Js
V = frequency of incident photon
Vo = threshold frequency
V = velocity of electron
me = mass of electron = 9.108 x 10-31 kg

Illustration of photoelectric
UV light (hv)
effect
Stream of
electrons

eeee-

e-

Ammeter to
measure current

Flow of electrons
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Photoelectric effect ...

When EM radiation with frequency above threshold frequency
(vo) is shined on the metal surface, an electric current registers
on the meter .
For frequency below the cut-off frequency (vo ), no current is
obtained, even at very high intensities.
As frequency increases above vo , the kinetic energy of electron
increases as illustrated below.

Kinetic
Energy
vo
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Frequency (v)
29

Calculations involving photoelectric effect

Example 3:
When sodium metal surface is exposed to radiation of 300 nm, electrons with kinetic
energy KE = 1.68 x 105 Jmol-1 are emitted.
a) Calculate the maximum energy needed to remove an electron from the metal
surface.
b) What is the maximum wavelength that will cause photoelectric effect?
Ans:
Step 1
Energy of photon = hv = hvo + KE = h x c/ + KE
= (6.626 x 10-34 Js) x (3 x 108 m/s) = 6.626 x 10-19 J
300 x 10-9 m
Step 2
KE of 1 electron
= KE of 1 e- in Jmol-1/Avogadros number
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30

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Calculations involving photoelectric effect ...

KE of 1 electron = 1.68 x 105 Jmol-1 = 2.789 x 10-19 J
6.022 x 1023 mol-1
hvo = Emin = hv - KE
= (6.626 x 10-19 2.789 x 10-19)J = 3.837 x 10-19 J
b) From Emin = hvo or Emin = hc/ we can determine max, i.e.


3.837 x 10-19 J = (6.626 x 10-34 Js) x (3 x 108 m/s)

-34
8

= (6.626 x 10 Js) x (3 x 10 m/s) /3.837 x 10-19 J
= 5.181 x 10-7 m
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1.4 Bohrs Atomic Model

Bohrs atomic model explains the
origin of the spectrum of
hydrogen and hydrogen-like
species e.g. He+, Li2+ etc.
Three main postulates of Bohrs
atomic model
1) Electron in an atom behaves like
a material particle and revolves
round the nucleus in a fixed
circular orbits or shells called
energy shells or energy levels

Electron in a particular shell is
associated with a certain
amount of energy.

Energy
increases with increasing
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distance from nucleus.

E1 < E2 < E3 etc.

The values of n (the principal
quantum number ) are n = 1 =
k, n= 2= L etc.
2) As long as the electron is
revolving in a particular orbit, it
does not absorb nor emit
energy. Hence, these energy
levels are also referred to as
stationary states.

When electron jumps from
lower energy n=1 with energy
E1 to higher energy n=2 with
energy E2, it absorbs energy in
form of photon.
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Bohrs Atomic Model ...

Energy change E = E2 E1 = hv = hc/

........................................................ Eq. 7

Where,

When electron falls from higher energy

level n=2 with energy E2 to lower energy
level n=1 with energy E1, energy is
emitted.
E = E2 E1 = hv = hc/ .............. Eq. 8
The released energy appears as a
spectral line in the emission spectrum.

3) Electron can only move in the orbits in

which the angular momentum (mvr ) of
the revolving electron is an integral
multiple of h/2

mvr
= nh/2 ............................. Eq. 9
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m = mass of electron = 9.108 x 10-31

kg
V = velocity of electron
r = radius of the orbit in which
electron is revolving
h = Plancks constant = 6.626 x 10-34
Js
n = an integral number which
denotes the number of orbit.
The equation mvr = nh/2 means
that the angular momentum of the
revolving electron is quantised which
implies that the magnitude of the
angular momentum is always a whole
33
number not fraction.

Bohrs Atomic Model ...

By applying the postulates and classical laws of physics, Bohr
was able to derive expressions for:
1)
2)
3)
4)

Energy of revolving electron

Velocity of revolving electrons
The radius of the nth orbit.
Frequency and wavelengths of spectral lines emitted.

Derivation of the expression for the radius of nth orbit of hydrogen

atom and hydrogen-like species.
Step1:
Considering hydrogen or hydrogen-like species with atomic number =
z,
Assuming electron of charge e- is revolving round the nucleus.
The charge on the nucleus will be = ze.
Assume r = the distance between the revolving electron and the
nucleus = radius of the orbit, m = mass of electron and V = tangential
velocity of electron
1.

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Bohrs Atomic Model ...

At any time, the electron experiences two types of forces:
1) Electrostatic force of attraction (centripetal force or CP)-the force of
attraction between the nucleus and the revolving electron.

1 x Ze2
4 r2

CP =

.......................................................... Eq. 10

Where, = permittivity constant of the media = 8.854 x 10-12 J-1C2m-1

2) Force of repulsion (centrifugal force or CF) the force acts outwards
from the nucleus hence keeps electron revolving away from the orbit.

CF = mv2/r ..........................................................................Eq. 11,

At any moment, Centrifugal force equals centripetal force

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Bohrs Atomic Model ...

1 x Ze2 = mv2
4
r2
r

V2 =

Ze2 x 1 ................................................Eq. 12
4
mr
From quantisation of angular momentum,

v2 = n2h2/42m2r2

mvr = nh/2

......Eq 13

Equating equation 12 and 13,

.............................Eq. 14
Ze2 x 1 = n2h2
4 mr 42m2r2

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Bohrs Atomic Model ...

Making r the subject,

r = n2h2 x 4 m
42m2 Ze2

r=

r=

n2h2
m e2 Z

h2 n2
m e2 Z

.............................................................................Eq. 15

Substituting the values of = 3.14; h = 6.626x10-34 Js; = 8.85

x 10-12J-1C2m-1; m = 9.108 x 10-31 kg; e- = 1.602 x 10-19 C
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Bohrs Atomic Model ...

Noting that J = kgm2s-2, the value of the radius of nth orbit
can be calculated as:
rn = n2 x (6.626x 10-34 Js)2 x (8.85 x 10-12J-1C2m-1)
3.14 x (9.108 x 10-31 kg) x (1.602 x 10-19C)2 x Z
= n2 x 5.29 x 10-11 x J2S2j-1C2m-1
kgC2 x Z

= n2 x 5.29 x 10-11 x Js2m-1

kg x Z

= 5.29 X 10-11 X n2 X kgm2s-2s2m-1

kg x Z
rn = 0.529 x 10-10 (n2/z) m ...............................................Eq. 16
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Relationship between rn and (r1)H

From equation 15,

rn =
h2 x n2
m e2 Z

(r1)H =

.....................................Eq. 17

h2 x 12 .........................................Eq. 18
m e2 1

Dividing equation 17 by Eq.18,

Rn/ (r1)H = h2

x n2 x me2 = n2
Z
h2
z

m e2

rn = (r1)H x n2
Z

or

rn = 0.529 x 10-10 x n2 m ..........Eq. 19

Z

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Relationship between rn and (r1)H ...

Example 5: Calculate the radius of 3rd orbit of hydrogen atom.
Ans. From equation 15,

rn =

h2 x n2
m e2 Z

0.529 x 10-10 x n2 m
Z

For n = 3 and Z = 1; we obtain the radius of the 3rd

orbit of H- atom given by,

(R3)H = 0.529 x 10-10 x 32 m = 4.761 x 10-10 m
1
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20

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Expression for velocity

revolving in the nth orbit

of

electron

Velocity of electron revolving in hydrogen atom and hydrogenlike species:

Noting that centripetal (1 x Ze2 )
4 r2 and centrifugal (mv2/r)
forces are equal;

Ze2 = mv2/r
4 r2

or

v2 = Ze2 ..........................Eq. 20
4 rm

From quantisation of angular momentum,

mvr = nh/2 or v =nh/2mr .......................................Eq. 21
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Expression for velocity of electron

revolving in the nth orbit cont.
Dividing Eq. 20 by Eq.21 ;

V2 =
Ze2
x 2mr = Ze2
v
4 rm nh
2 nh

Ze2
.....................................................Eq. 22
2 nh
Substituting the values of constants,
e- = 1.602 x 10-19C, = 8.85 x 10-12 J-1C2m-1 and h = 6.626 x
10-34 Js
Vn =
Z x (1.602 x 10-19C)2
.
2 x (8.85x10-12 J-1C2m-1) x n x (6.626 x 10-34 Js)

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Vn =

42

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Expression for velocity of electron

revolving in the nth orbit cont.
Vn = 0.2185 x 107 Z ms-1 ...................................................Eq. 23
n
Number of revolutions made by electron moving in the nth orbit
Number of revolutions =

Vn ........................................Eq.24
2rn

From Eq. 22 and 23 Velocity of e- = Vn = Ze2 = 0.2185 x 107 Z ms-1

2 nh
n
From Eq. 15 and 16,
radius of nth orbit = rn = h2 n2 = 0.529 x 10-10 x n2 m
m e2 Z
Z
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Expression for velocity of electron

revolving in the nth orbit cont.
Assuming that an atom is circular (Bohrs Theory),
No. of revolutions = (0.2185 x 107 Z ms-1)x (
z
.)
-10
2
n
2 x 0.529 x 10 x n m

No. of revolutions = 65.711 x 1014 x Z2 s-1 ...........................Eq. 25
n3

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22

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Calculating Energy of electron in nth Orbit

of H-atom and hydrogen-like atoms
The sum energy of electron (En) = Potential Energy (PE) +
Kinetic Energy (KE)

En = mv2 Ze2/4 r .............................................. Eq. 26

For e- revolving in nth orbit, centripetal and centrifugal forces are
equal (from Eq. 20),

Ze2 = mv2/r or mv2 = Ze2 or mv2 = Ze2 .....Eq. 27
4 r2
4 r
8 r

Substituting Eq. 27 into Eq. 26 for kinetic Energy,
=


En = Ze2
Ze2
- Ze2 .................................Eq. 28
8 r
4 r
8 r
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Calculating Energy of electron in nth Orbit

of H-atom and hydrogen-like atoms cont.
h2 n2 from equation 15,
m e2 Z

Substituting r with

En = - Ze2 x
8

m e2 Z = - m e4
h2 n2

Z2 ............................Eq. 29

8 2 h2 n2

Where, m = 9.108 x 10-31 kg, e- = 1.602 x 10-19 C,

= 8.85 x 10-12 J-1C2m-1, h = 6.626 x 10-34 Js, J = kgm2s-2
Substituting the values of constants,
En = -(9.108x 10-31kg) x (1.602 x 10-19 C)4
x Z2
8 x (8.85 x 10-12 J-1C2m-1)2 x (6.626 x 10-34 Js)2 n2
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Calculating Energy of electron in nth Orbit

of H-atom and hydrogen-like atoms cont.
En = -2.18 x 10-18 x Z2

kgC4

n2
(J-1C2m-1)2 (Js)2
kgC4
En = -2.18 x 10-18 x Z2 x
n2
J-2C4m-2J2s2
En = -2.18 x 10-18 x Z2 x kgm2s-2
n2

Energy of electron
increases with increasing
energy level

En = -2.18 x 10-18 x Z2 J atom-1 ...................................................Eq. 30

n2
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Relationship between En and (E1)H

From Eq. 29,
En = - m e4 Z2
8 2 h2 n2
Dividing En by (E1)H ,

En
= - m e4 Z2
(E1)H
8 2 h2 n2

(E1)H = - m e4 x 12
8 2 h2 12
x

- 8 2 h2 12
m e4 12

= Z2
n2

En = (E1)H x Z2 .......................................................Eq. 31
n2

Substituting the values (E1)H from equation 30,
En = - 2.18 x 10-18 x Z2/n2 J atom-1

The negative energy implies as e- approaches the nucleus, E is
released hence energy of e- decreases.

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Calculating ionisation (IE) energy of Hatom hydrogen like species

IE is defined as the energy involved in exciting an e- from the
lowest energy level to infinity (n = ).
E1 = - me4
Z2
8 2 h2 n2

= -2.18 x 10-18 J atom-1

E = - me4
Z2 = -2.18 x 10-18 J atom-1 = 0
8 2 h2 (N)2
(N)2
IE = E = E - E1
Ionisation energy increases
across the period and
= 0 - (- 2.18 x 10-18 Z2 J atom-1
decreases down the group.
n2
IE
= 2.18 x 10-18 Z2 J atom-1 .........................................Eq. 32
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n2

Calculating wavelength() and frequency

(v) of spectral lines cont.
When electron falls from higher orbit (n = 2) to a lower orbit (n =
1) H emission spectrum is produced.
The spectrum consists of a large number of spectral lines
grouped into 5 series i.e. Lyman, Balmer, Paschen, Bracket &
Pfund series

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Calculating wavelength() and frequency

(v) of spectral lines cont.
Step1: Determine the energy
change.

Step 2: Determine frequency

Assuming electron from n=2 to n=2;

For n1, E1 = - me4 x Z2
8 2 h2
n 12

For n2, E2 = - me4 x Z2

8 2 h 2 n 22

E = E2-E1 = - me4 x Z2 - (-me4 x Z2 )

82 h2 n22 82 h2 n12

E = E2-E1 = me4 x Z2 x ( 1 - 1 )
8 2 h2
n12 n22
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.................................Q33

But E = hv
hv =
me4 Z2 x( 1 - 1)
8 2 h2 n12 n22
v =

me4 x Z2 x( 1 - 1 )
8 2 h3
n12 n22

..............................................................Q34

Substituting the values of constants:

Note, m = 9.108 x 10-31 kg, e- = 1.602 x
10-19 C, = 8.85 x 10-12 J-1C2m-1,
51
h = 6.626 x 10-34 Js, J = kgm2s-2

Calculating wavelength() and frequency

(v) of spectral lines cont.

Substituting the constants,

me4
= 3.2906 x 1015 s-1
8 2h 3

V = 3.2906 x 1015 Z2 x (1 - 1 ) s-1 or
n12 n22
Hz .....................................Eq. 35
Step 3: Determine wave numbers
From Equation 3 and Eq. 34,

v = 1/ = v/c = me4 x Z2 x (1 - 1 )
8 2 h3c n12 n22

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But the expression me4

8 2 h3c
is called Rydberg constant of hydrogen
atom = 1.0976 x 107 m-1
Thus, v = 1.0976 x 107 Z2 ( 1 - 1 )
n12 n22
2
=
RH Z (1 - 1 )
n12 n22
But from Eq. 34 , V = me4 x Z2 x (1 - 1 )
8 2 h3 n12 n22

V = me4 x c x Z2 x ( 1 - 1 )
8 2 h3 c
n12 n22
52

26

02/10/2012

Calculating wavelength() and frequency

(v) of spectral lines cont.
me4
=
2
3
8 h c
Thus, V = RHc Z2 ( 1 - 1 ) s-1 or
Hz ...Eq. 37
n12 n22

Rydberg constant, RH

Step 4: Determine wavelength ()

From 1/ = v = v/c , the value of
can be calculated as,

= c/v = 1/ v

Calculate the frequency, energy and wavelength

of the radiation corresponding to the spectral
line of the lowest frequency in Lyman series in
the spectrum of H-atom.
Ans.
From 1/ = v = RH (1 - 1 )
n12 n22
The lowest line in the Lyman series
corresponds to e- moving from n = 2
to n = 1.
From Eq. 36,

v = 1/ = v/c = me4 x Z2 x (1 - 1 )
8 2 h3c n12 n22
.........................................................Eq. 36

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53

Example cont.
= (1.09678 x 107 m-1) [1/12 1/22] = 1.09678 x 107 m-1 x

4
=
7
-1
3 x 1.09678 x 10 m

1.215 x 10-7 m

Frequency, v = c/ = 3 x 108 m/s = 2.46 x 1015 s-1

1.215 x 10-7 m

Change in energy = E = hv = me4 x c x h x Z2 x ( 1 - 1 )
8 2 h3 c
n12 n22
= RH x c x h x Z2 x ( 1 - 1 )
n12 n22
= 1.09678 x 107 m-1 x (6.626 x 10-34 Js)x (3 x 108 ms-1) x
= 16.34 x 10-19 J
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54

27

02/10/2012

Bohrs Atomic model

A : Achievements

1) Explained the
stability of atom
2) Explained how
emission spectrum is
produced
3) Explained how
absorption spectrum
is produced
4) Explained the origin
of spectral lines in
hydrogen spectrum
eg. Lyman, Balmer,
Paschen, Bracket
and Pfund series
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B: Limitations

1) It does not explain the origin of spectra

given by multi-electron species.
2) It assumes the circular orbits in which
the electrons revolve are planar instead
of 3 dimensional.
3) It does not explain the cause of Zeeman
and Stark effects:
1) Zeeman effects- splitting of spectral lines in
magnetic field
2) Stark effect - splitting of spectral lines in
electric field

4) It does not account for uncertainty

principle and dual nature of electrons.
5) It does not explain the origin of fine
structures observed in the spectral lines
55
using high resolution microscope.

Wave Mechanical Concepts of Atomic

structure
The theory assumes that all small particles such as electrons,
protons, neutrons and atoms when in motion possess wave
properties such as wavelength (), amplitude (A), and frequency
(v ).
De Broglie derived expression describing the relationship
between the wavelength associated with the mass m of a body
moving with velocity v.


= h/mv ..................................................................Eq. 37

Where = wavelength of the particle, h = Plancks constant, v =
velocity of the particle and m = mass of the particle.
02/10/2012

56

28

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Wave Mechanical Concepts of Atomic

structure cont.
Derivation of De Broglies equation
From Plancks E = hv,
From Einsteins equations of energy,
E = mc2 .......................................................Eq. 38
Equating the two expressions,


mc2 = hv = hc/


mc = h/

= h/mc = h/p

Where p = momentum of the particle.
Implication of De Broglies Equation
1)
2)

Everything in nature possesses both wave and particle properties.

Properties of large particles are well characterised by particle properties
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whereas for small objects wave properties are suitable.

57

Examples of calculations involving De

Broglie's equation
Calculate the wavelength of a ball of mass 100 g moving with velocity of 1000 cm/s
and that of an electron moving at velocity of 2.188 x 10-8 cm/s.
Ans:
i) = h/mv = 6.626 x 10-34 Js = 6.626 x 10-34 m
0.1 kg x 10 m/s
ii) For an electron, = h/mv = 6.626 x 10-34 m
9.108 x 10-31 kg x 2.188 x 10-10 ms-1
= 3.32 x 10-10 m
The wave length of the ball is too small to be measured by
spectroscopic techniques, whereas that of electron is comparable
with that of X-ray and hence can be measured.
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58

29

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Heisenbergs Uncertainty Principle

It states that both position and momentum of the particle
cannot be determined with absolute exactness or certainty.

If momentum or velocity of the particle is accurately
determined, the measurement of position will be less precise.
e- changes momentum at
the instant of collusion

Photon

Expected path of the electron

eMomentum of e- changes when
a photon of light strikes it.
+
Nucleus
02/10/2012

59

Heisenbergs Uncertainty Principle cont.

The uncertainty in measurement of position (x) and
uncertainty in determining momentum (p) or velocity (mv)
is given by Heisenbergs expression,
x x p h/4 ...........................................................Eq. 39
or x x m v h/4 ...................................................Eq. 40
Example:
A cricket ball of mass 200g has uncertainty in position of 5 pm. Calculate
uncertainty in the velocity of the ball.
Ans: x x p = h/4 or x x m v h/4 ; Thus v = h/4 m x
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60

30

02/10/2012

Heisenbergs Uncertainty Principle cont.

v x 5 x10-12 m x 0.2 kg = 6.626 x 10-34 Js /4 x 3.14

v = 6.626 x 10-34 Js
.
5 x 10-12 m x 0.2 kg x 4 x 3.14

= 0.5275 x 10-22 x Js
m x kg

v = 5.275 x 10-23 x kgm2s-2s

= 5.275 x 10-23 m/s
m x kg

Example: According to Bohrs theory of H-atom, the velocity of an electron in
the first orbit is 2.183 x 106 m/s. If uncertainty in position of electron is 5 pm,
calculate the uncertainty in velocity.
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61

Heisenbergs Uncertainty Principle cont.

x x p h/4 or x x m v h/4

5 x 10-12 m x 9.108 x 10-31 kg x v = 6.626 x 10-34 Js
4 x 3.14

v
= 6.626 x 10-34 Js
=
1.158 x 107 ms-1
5 x 10-12 m x 9.108 x 10-31 kg
Explanation:
Uncertainty in velocity of the cricket ball is very small compared to
the actual velocity that an object of this size can have. Hence for
macroscopic objects, both velocity and position can be determined
with accuracy.
The uncertainty in velocity of electron in the first orbit is greater than
the velocity of electron in the orbit.

For microscopic objects, it is not possible to simultaneously
determine
both position and velocity of the particle with accuracy.
02/10/2012
62

31

02/10/2012

Schrondingers Wave Equation

Is based on the assumption that if electron behaves like a
wave, there must be a wave equation describing its motion.
Schrodingers equation describes the position of electron in
three dimensional space around the nucleus.
If we represent a wave by the sine function,
then, = A sin (2x/) ..................................................Eq.41
Where A = amplitude of the wave, x = displacement from the
origin, = wavelength of the wave.
Differentiating the equation 41 twice with respect to (wrt) x,
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63

Schrondingers Wave Equation cont.

/x = A(2/) cos (2x/)
2/x2 = (-42/2)A sin(2x/) = - (42/2) ...........................Eq. 42
Noting that total Energy E = PE + KE = V + mv2

2E = 2V +mv2 .......................................................................Eq. 43
Making v2 the subject,

V2 = 2(E V)/m ......................................................................Eq. 44

V=
2(E-V)/m

From De Broglies equation,

= h/mv = 2 = h2/m2v2 ........................................................Eq. 45
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64

32

02/10/2012

Schrondingers Wave Equation cont.

Substituting for v2,

2 = h2/m2 x m/2(E-V) = h2/2m(E-V) .............................Eq. 46

Substituting Eq. 46 into Eq. 42

2/x2 = - (42/2) = (42 2m(E-V)/h2)

2/x2 + 82 m(E-V)/h2) = 0 ....................................Eq. 47

This is the wave equation for a particle moving along the x axis.

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65

Schrondingers Wave Equation cont.

For 3 dimensional space,

2/x2 + 2/y2 + 2/z2 + 82 m(E-V)/h2) = 0 ...........Eq. 48

This is the Schrodingers equation

The equation can be further reduced to,

2 + 82m (E-V) = 0 ............................................Eq. 49

h2
Where, 2 = 2/x2 + 2/y2 + 2/z2 and is called the Laplacian
operator
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66

33

02/10/2012

Schrondingers Wave Equation cont.

The equation 49 can be rearranged into,
(V- 2h2) = E
82m
Or H = E ........................................................................Eq. 50
Where H = V - 2h2/82m is called the quantum mechanical
Hamiltonian Operator, and E is the Eigen value.
The equation is called Schrodinger equation in operator form, and
the corresponding wave function is called Eigen function.
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67

Significance of the wave function ()

The wave function (psi) can be negative or positive, thus it has
no practical significance since the probability of finding an
electron can only be positive or zero.
The wave function squared (2) is always positive, hence gives the
probability of finding an electron around the nucleus.

Solutions to Schrodinger equation

Solving the schrodinger equation for each electron gives the
shape of atomic orbital, which is defined as the three dimensional
space in which the probability of finding electron is maximum.

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68

34

02/10/2012

Differences between an orbit and atomic orbital

Orbit

Atomic orbital

1. Is a definite circular path at a fixed

distance from the nucleus in which electron
revolves

1. A 3 dimensional region or space around

the nucleus within which the probability of
finding electron with a definite energy is
maximum.

2. It indicates the exact position of an

electron in an atom

2. Does not specify definite position of

electron in the tom since electron due to
wave nature cannot be at fixed distance
from the nucleus

3. There is certainty about movement of

electron in an orbit

3. No certainty about movement of an

electron in an orbital

4. It represents planar motion of electron

It represents 3 dimensional motion of

electron

5. Maximum number of electrons in orbit =

2n2 where n = number of orbit

5. Maximum number of electrons in an

orbital = 2, the two must have opposite
spins

6. Orbits are circular in shape

6. Orbitals have different shapes e.g. Sorbitals are spherical, p-orbitals are egg
shaped etc.

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69

Quantum numbers
These are integral numbers that describe:
1)
2)
3)
4)

the energy of electron in an orbit,

The position of electron from the nucleus
Shape and the number of orientations of orbital round its own
axis
Orientation of the spinning of electron round its own axis

There are four types of quantum number i.e.

1)
2)
3)
4)

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The principal quantum number (n)

Azumuthal quantum number (l)
Magnetic quantum number (m)
Spin quantum number (s)

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35

02/10/2012

The principal quantum number (n)

1) It represents the number of shells (orbit) or main energy level in
which the electron revolves round the nucleus e.g. n = 1; 2; 3 e.tc.
2) It gives the distance of the electron from the nucleus (radius of the
orbit) e.g. r

h2 n2

m e2 Z
3) It gives the energy (E) of an electron in an orbit i.e.
En = - m e4 Z2
8 2 h2 n2
4) It gives the maximum number of electrons that can be
accommodated in a given shell, i.e. maximum number of electrons
= 2n2
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71

Azimuthal Quantum Number (l)

It determines the magnitude of the orbital angular momentum
hence also called orbital angular momentum quantum number.
It explains the appearance of the group of closely spaced lines in
the hydrogen spectrum.
It is disgnated by l
It assumes values from 0, 1, 2 ... (n-1)

e.g. For n = 3, l = 0, 1, 2.
The values of l represent a particular sub-shell within the principal
shell i.e.
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72

36

02/10/2012

Azimuthal Quantum Number (l) cont.

Examples:
For l = 0
s-sub-shell (or s- orbital)
l = 1 p- sub-shell (or p-orbital)
l= 2
d- sub-shell (or d-orbital)
l= 3
f- sub-shell (or f-orbital)
The letters s, p, d and f are obtained from the description of the
spectral lines i.e. Sharp, principal, diffused and fundamental
respectively.
The total number of sub-shells in a given shell equals the number
of the main shell e.g. for n = 1, the only sub-shell is s; for n = 2,
two sub-shells present are s and p etc.
02/10/2012

73

Azimuthal Quantum Number (l) cont.

The maximum number of electrons that can be accommodated
in a given subshell = 2(2l +1)
Example:

02/10/2012

Orbital

Value of l

2(2l +1)

10

14
74

37

02/10/2012

Magnetic Quantum Number or

orientation quantum number (m)
It explains the presence of additional spectral lines seen when
magnetic field is applied to the source of spectrum
It gives the total number of orbital orientations within a given subshell.
It takes values from l, 0, +l
Example:
l = 0; m = 0
l = 1; m = -1, 0, +1
l = 2; m = -2, -1, 0, +1, +2
l = 3; m = -3, -2, -1; 0; +1; +2; +3
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75

Spin Quantum Number (s)

Arises due to the fact that electron while moving round the
nucleus also rotates around its own axis.
The spinning can be in clockwise or anti-clockwise direction.

Representation of electron spinning:

1) Clockwise (+ ) or ( ) or ( spin)
2) Anticlockwise (- ) or ( ) or ( spin)
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76

38

02/10/2012

Relationship between quantum numbers

Principal
Quantum
number (n)

Values of l
Total
Different
and number Number of
values of m
of sub-shells electrons in
a sub-shell =
2(2l+1)

Max
number of
electrons in
orbital = 2 x
number of
orbitals

Max
number of
electrons in
main shell =
2n2

0
2 (2x0 +1) =
(s -sub-shell) 2

2x1=2

2 x 12 = 2

0
(2s orbital)
1 (2 porbital)

2 (2x0 +1) =
2
2(2 x 1+1) =
6

2 x 1= 2

0 (3 sorbital)
1 (3 porbital)
2 (3 dorbital)

2(2x0+1) = 2 0

2x1=2

2(2x1+1) = 6 0; -1;+1

2x3=6

2(2x2+1) =
10

2 x 5 = 10

2 x 22 = 8
0; +1; -1

0; -2; -1; +1;

+2

2x3=6

2 x 32 + 18

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77

Types of atomic orbitals

Atomic orbitals have different shapes
1) s-orbitals
They are symmetrical in shape and non-directional and occur
when l = 0; m = 0; n 1
Accommodate maximum of 2 electrons
For larger values of n, the size of s-orbital increases i.e. The
number of radial nodes increases
A node is a region in space where the probability of finding an
electron is zero. At a node, 2 = 0
For an s-orbital, the number of nodes is (n - 1).
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78

39

02/10/2012

s- orbitals

79

P- Orbitals
Occur when l = 1; m = -1; 0; +1; n 2
There are three p-orbitals px, py, and pz. (The three p-orbitals lie
along the x-, y- and z- axes of a Cartesian system. The letters
correspond to allowed values of ml are -1, 0, and +1.)
Each has two egg shaped lobes on each side of the nucleus
The probability of finding electron in each lobe is the same e.g.
Degenerate orbitals (same energy level)
Both lobes are separated by nodal plane which passes through the
nucleus. The electron density on the plane and the nucleus is zero.

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80

40

02/10/2012

d-Orbitals
Occur when n 3; l = 2; m = -2; 1; 0; +1; +2
They are dumb-bell shaped
All the five orbitals are
degenerate
Three of the d-orbitals lie in a
plane bisecting the x-, y- and zaxes, the remaining two lie in a
plane aligned along the x-, yand z-axes.
Four of the d-orbitals have four
lobes each, but one has two
lobes and a collar.
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81

f-Orbitals
They occur when n 4; l = 3; m = -3; -2; -1; 0; +1; +2; +3
There 7 types of f-orbitals
Almost no covalent bonding because metal orbitals are so
contracted
Radial functions same for all nf orbitals
Three angular nodes (nodal planes) orthogonal to s, p and d
orbitals

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82

41

02/10/2012

Electron configuration
This is the distribution of electrons into different atomic orbitals in
order of increasing energy levels. It shows in which orbitals the
electrons for an element are located.
The filling of atomic orbitals follow 3 principles@
1) Paulis exclusion principle
2) Aufbaus principle
3) Hunds rule of maximum multiplicity

1) Pauls exclusion principle

It states that no two electrons in an atom can have the same set
of the four quantum numbers e.g.

For two electrons in the same orbital, the spin quantum number
must be different i.e. Spinning in different directions
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83

Electron Spin and the Pauli

Exclusion Principle
Since electron spin is quantized, we
define ms = spin quantum number =
.

Two electrons in the same orbital

must have opposite spins.

S = -1/2

S = +1/2

84

42

02/10/2012

Pauls exclusion principle cont.

Main
shell (n)

Combin Different Values of n, l, m,

ation
and s
number

Electron
with upward
and
downward
arrows

Total
number of
electrons in
orbital

Total
number of
electrons in
main shell

1
2

N = 1; l= 0; m= 0; s= +1/2
N = 1; l = 0; m = 0; s = -1/2

2 (1s2) () 2 x 12 = 2

N = 2; l= 0; m= 0; s= +1/2

2 (2s2) () 2x22 = 8

N = 2; l = 0; m = 0; s = -1/2

N = 2; l = 1; m = 0; s = +1/2

N = 2; l = 1; m = 0; s = -1/2

N = 2; l = 1; m = +1; s = +1/2

N = 2; l = 1; m = +1; s = -1/2

N = 2; l = 1; m = -1; s = +1/2

N = 2; l = 1; m = -1; s = -1/2

2 (2pz2)
()

2 (2py2)
()

2 (2px2)
()

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85

Aufbau Principle
Also referred to as the building up principle
Each added occupies higher energy sub-shells only after the
lower sub-shells have been filled completely
The energy of orbital is determined by the n+l rule
1) Orbital having lower value of n+l will have lower energy e.g.
2s< sp
2) Orbitals having similar (n+l) values, the orbital with lower
value of n will have lower energy eg. 3p<4s
02/10/2012

86

43

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Orbitals in Many Electron Atoms

Order of filling atomic orbitals

Energy levels of orbitals

87

Hunds Rule of Maximum Multiplicity

single electrons with same spin occupy each equal-energy
orbital before additional electrons with opposite spins can
occupy the same orbitals

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88

44

02/10/2012

Short form of electron configurations

For shorthand electron
configurations
Write the core electrons
corresponding to the filled
Noble gas in square brackets.
Write the valence electrons
explicitly.

Example,
P: 1s22s22p63s23p3 but Ne is
1s22s22p6
Therefore, P: [Ne]3s23p3.

For atoms having having p, d

and f orbitals, the most stable
electron configuration is when
the d and f orbitals are half or
fully filled.
Example:
Cu (Z = 29)
Stable ec: = 1s2, 2s2, 2p6, 3s2,
3p6, 4s1, 3d10
Cr (Z = 24)
Stable ec: = 1s2, 2s2, 2p6, 3s2,
3p6, 4s1 3d5
89

Definitions
Outermost shell: is the shell with maximum number of n value
that is fully or partially filled. Also called valence shell, and
electrons in this shell are called valence electrons
Inner shells: are the shells other than the valence shell. The total
number of electrons in the inner shells are called core electrons
or kernel electrons
Penultimate shell: this is the shell just before the valence shell
i.e. (n-1)nth shell, where n represents the valence shell.
Antepenultimate shell: this is the (n-2)nth shell where n refers to
the valence shell.
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90

45

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Effective Nuclear Charge

Effective nuclear charge: is the net charge experienced by an
electron in a many-electron atom.
It is not the same as the charge on the nucleus because of the
effect of the inner electrons.
It results from the degeneracy of the orbitals with the same
value of n.
In a many-electron atom, for a given value of n, the effective
nuclear charge decreases with increasing values of l.
Z eff = Nuclear Charge (Z) Screening Constant ()

Z eff = Z - ................................................Eq. 51
91

Screening and Penetration

The effects of other electrons in an atom on an electron is
screening the positive charge. Since electrons are waves,
they penetrate into space occupied by other electrons. No
assumption can be made so that we can treat manyelectron atoms as H-like atoms.
Thus, we assume the charge experienced by an electron as
Zeff, the effective atomic charge (or number).
Thus, the energy of many electrons is

for H

Zeff2
En = RH ---------;
n2

RH = 13.6 eV, the Rydberg costant

Energies of sub-shells are also affected by the quantum

number l, as we have pointed
out before, but quantum
Period Table
numbers l and m also affect sizes.

92

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02/10/2012

Calculation of effective nuclear charge

Calculation of the effective nuclear charge is based on the Slates
rules:
1) Determination of the nuclear charge for electron in s and p
orbitals:
The value of for electron in s or p orbital of the nth shell of an
atom or ion is the sum of the following:
1) Each electron in nth shell contributes 0.35 to the value of
2) Each electron in the (n-1)th shell contributes 0.85 to
3) Each electron in the (n-2)th shell and inner shells contributes 1
to the value of
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93

Calculation of effective nuclear charge

4) No contribution to the value For Cu,
of by electron in (n+1)th
EC: 1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d10
shell and the shells above
Rearranging: (1s2, 2s2, 2p6), (3s2,
3p6, 3d10) ,(4s1)

5) If being calculated is for

electron in 1s orbital, the
remaining electron
= (1x 10)+(0.85x 18) + (0.35x 0)
contributes 0.3 to the value
= 25.30
of
Example:
1. Calculate the values of and Z eff = Z -
= 29 25.30 = 3.70
Zeff for 4s and 3d electrons in
a)

Mn; Cu ; Cr

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94

47

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Calculation of effective nuclear charge for

electron in d-0rbital
The value of is the sum of the
following:
a) No contribution to by
electron in the nth orbital
b) Each electron in the (n-1)d
orbital contribute 0.35 to the
value of
c) Each electron in the (n-1)s, (n1)p orbitals and inner shells
contribute 1 to the value of
Examples:
Calculate the value of and
zeff for electron in 3d orbital
of: Cu; Mn ;Cr

For Cu,
EC: 1s2, 2s2, 2p6, 3s2, 3p6, 4s1,
3d10
Rearranging: (1s2, 2s2, 2p6, 3s2,
3p6 ) (3d10) ,(4s1)
= (1x 18)+(0.35x 9) + (0x 1)
= 21.15
Z eff = Z -
= 29 21.15 = 7.85
95

Electron
Configurations
Periodic Table

and

the

96

48

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Characteristics of s-block elements

These are elements in which the last electron fills the s-orbital
They are located at the extreme left of the periodic table
(Group IA and IIA)
They consist of high electropositive metals
The valence shell configuration is ns1-2
The outer shell is partially filled

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97

Characteristics of p-block elements

The occur on the extreme right hand of the Periodic Table
The nth shell of the noble gases is completely filled
The (n-1)th shell of p-block elements of the 3rd period has 8
electrons, whereas that of the 4th, 5th and 6th periods has 18
electrons
The (n-2)th shell of p-block elements of the 5th has 18 electrons
whereas that of the 6th has 32 (18+14) due to the inclusion of 14
Lanthanides
The 2nd shell of the p-block elements has 3 electrons whereas the
3rd other periods has 8 electrons. The 1st shell of this block has 298
02/10/2012
electrons

49

02/10/2012

Characteristics of d-block elements

They occur between s and p block elements
The general electron configuration is ns p(n-1)d1-10
General characteristics d block elements
They often form coloured compounds
They can have a variety of different oxidation states
They are often good catalysts e.g. Mn, Fe, Co, Cr
They are silvery-blue at room temperature (except copper and
gold)
5) They are solids at room temperature (except mercury)
6) They form complexes
7) They are often paramagnetic.

1)
2)
3)
4)

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99

Characteristics of f-block elements

1) Lanthanides
1) Silvery metals.
2) High melting points.
3) Found mixed in nature and
hard to separate.
4) Used in:
Movie projectors
Welders goggles
TV and Computer monitors

2) Actinides
1) Radioactive elements.
2) Only 3 exist in nature.
3) Remaining are synthetic
(transuranium elements)
greater atomic number
than uranium.
4) Decay quickly.
5) Used in:
Home smoke detectors,
nuclear power plants.

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Atomic properties
These are properties that change from one
element to the other, hence used to
characterise elements
1)
2)
3)
4)
5)
6)

Atomic radius
Ionization energy
Electronegativity
Electron affinity
Magnetic properties
Acidity and alkalinity of oxides

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Ionization Energy
The first ionization energy, I1, is the amount of energy required
to remove the first outermost electron from a gaseous atom:
Na(g) Na+(g) + e-.
The second ionization energy, I2, is the energy required to
remove the second outermost electron from a gaseous ion:
Na+(g) Na2+(g) + e-.
The larger the ionization energy, the more difficult it is to
remove the electron.
There is a sharp increase in ionization energy when a core
(non-valence) electron is removed.
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Ionization Energy
Periodic Trends in Ionization Energy
Ionization energy decreases down a group.

This means that the outermost electron is more readily
removed as we go down a group.

As the atom gets bigger, it becomes easier to remove an
electron from the most spatially extended orbital.
Ionization energy generally increases across a period.
As we move across a period, Zeff increases.

Therefore, it becomes more difficult to remove an
electron.
103

Trend in Ionization Energy

Ionization energy, I, is the energy required to convert a
gaseous atom or ion into a gaseous ion, in eV per ion or
in J or kJ per mole. For example,
Mg (g) Mg+ (g) + e; I1 = 738 kJ / mol = 7.65
eV/atom
Mg+ (g) Mg2+ (g) + e;
15.0 eV/atom

I2 = 1451 kJ / mol =

The effective atomic number Zeff, may be estimated using,

Zeff2
Eeff = --------a positive value
n2
But ionization energy is not Eeff.

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Variation of I1 as Z Varies
How does
first ionization
energy I1
vary in a
group and in
a period,
why?
Decreases
and
increases
respectively

Period Table

105

The In of Group n

Period Table

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Trends in periodic table atomic radius

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Electron Shells and the Sizes of Atoms

Electron Shells in Atoms
Consider a simple diatomic
molecule.
The distance between the two
nuclei is called the bond
distance.
If the two atoms which make up
the molecule are the same, then
half the bond distance is called
the covalent radius of the atom.

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Atomic radii as Z increases

Period Table

109

From Atoms to Ions

arrange the following lists by increasing atomic radius.

Na+, Li+, K+, Cs+, Xe, IBr , Cl , I , F
Be2+, Li+, B, C, O2, F, N
Period Table

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Trends of Ionic radii

Iso-electrons: these are ions of different elements with
same electron configuration but different ionic sizes
Ions usually have the same electronic configuration as an
inert gas.
He
Li+

Be2+

N3

O2

Ne

Na+

Mg2+

P3

S2

Cl

Ar

K+

Ca2+

Se2

Br

Kr

Rb+

Sr2+

Te2

Xe

Cs+

Ba2+

Period Table

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Electron Affinity
Electron affinity is the opposite of ionization energy.
Electron affinity is the energy change when a gaseous atom
gains an electron to form a gaseous anion:
Cl(g) + e- Cl-(g)
Electron affinity of different in eV per ion or in J or kJ per mole.
For example,
F (g) + e F (g);

EA = 328 kJ / mol = 3.4 eV/atom

Li (g) + e Li (g);

EA = 59.6 kJ / mol = 0.62 eV/atom

O (g) + e O (g);

EA1= 141 kJ / mol = 1.46 eV/atom

O (g) + e O2 (g); EA2 =

744 kJ / mol =

7.71 eV/atom

The variation of EA is very irregular as Z increases. There is no particular trend in

groups and in periods.
Note the relationship of EAs and Is.

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Electronegativity
This is the ability of an atom to attract the shared electrons
towards itself.
This creates a partial negative charge on a more
electronegative atom and a partial positive charge on a less
elctronegative atom, hence the bond is polarised

Cl

Electronegativity cont.

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Magnetic Properties
Materials can be divided into three types according to
their magnetic properties. Be able to explain these terms:
Diamagnetic material: substance slightly repelled by a
magnetic field. There are no unpaired electrons.
Paramagnetic material: substance slightly attracted by a
magnetic field. There are some unpaired electrons,
(single e in an orbital)
Ferromagnetic material: substances strongly attracted
by magnetic field. Magnetic domains line up in these type,
Fe, Fe2O3 etc.
Which of these are paramagnetic, H, Na, Mg, Cl, Cl , Ag, Fe
Period Table

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Oxides and Strong Acids

Aside from HCl, other strong acids are derived from
oxides of N, S, Cl:
HNO3 H2SO4 HClO4
HClO3
Some oxides also form weak acids:
HCO3

HNO2 H2SO3 HClO2

In contrast, look at some strong

bases
NaOH
KOH
Ca(OH)2
RbOH Sr(OH)2
CsOH Ba(OH)2
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