General & Inorganic Chemistry

FME 151/FBE 105/FCE 181

Dr. Ruth Odhiambo

Department of Chemistry,
University of Nairobi
P. O. Box 30197-00100,
Nairobi, Kenya

Examination Center Building

Room G03

Email: odhiambor@uonbi.ac.ke; raodhiambo@gmail.com

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 Course Outline
1) Atomic structure:
– Electromagnetic radiation & Atomic structure
– Bohr’s atomic model & wave concept model of atomic
structure;
– electron configuration & effective nuclear charge
– Periodic table & atomic properties
2) Chemical bonding:
– Types of chemical bonds: ionic bond, covalent bond, metallic
bond, dative bond, hydrogen bond & van-der Waals bond.
3) Chemical kinetics:
– Rate of reactions and rate equations, factors that influence
rate of reaction, order of reaction, activation energy

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 Course content cont.
4) Chemical equilibrium:
– Equilibrium law, Equilibrium constant, homogeneous
equilibrium, heterogeneous equilibrium, Lechatelier’s principle.
5) Solutions:
– Types of solutions, Henry’s 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:
– Ammonia, nitrates, phosphates, sulfates, silicates, chlorine,
oxygen, ozone, carbon, etc).
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 Examination

• Two CATs = 15%

• 6 Practicals = 15%

• Final Exam = 70%

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 TOPIC 1: ATOMIC
STRUCTURE

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 1.1 Composition of an atom
Particle Symbol Charge Charge (C) Mass (Atomic Mass (kg)
mass units)

Proton p + +1.6 × 10-19 C 1 1.673 x 10-27

Electron e- - -1.6 × 10-19 C 1/1837 9.108 x 10-31
Neutron n 0 0 1 1.675 × 10-27

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16/02/2018 7
 1.2 Spectroscopy & Electromagnetic
radiation
a) Definition:
• Spectroscopy: The study of the interaction of electromagnetic
radiation with matter.

• Electromagnetic radiation: This is radiation consisting of waves of

radiant energy moving in the direction of propagation and
perpendicular to electric and magnetic fields.

• Emr plays an important role in understanding the atomic structure

and secondly they are themselves energy (light is energy) – Hence
they are used to investigate the amount of energy absorbed or
emitted by matter
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 Electromagnetic radiation
• The fact that they are energy means that they contain
momentum and therefore are particles in motion.

• The electromagnetic radiations consist of ‘particles’ or

‘packets’ of energy known as photons.

• They also have properties that are wave-like and can be

expressed as waves, hence the term electromagnetic
waves.

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 Characteristics of 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 of
propagation.

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 Characteristics of Emr Contd..

Direction of propagation

• The Emrs only differ in wavelength and frequency

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 b) Properties of Emr waves
1. Wavelength (symbol = λ pronounced as “lambda”): The
distance between two consecutive peaks in the wave.

1 m = 109 nm = 1010 Å = 1012 pm

nm = nanometre; = angstrom
pm = Pico-metre
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 Properties of Emr waves Contd..

2) Frequency (symbol = ν , pronounced as “nu”): This is the

number of waves or cycles that pass a point on the x-axis
each second. SI unit is Hertz (Hz = s-1)

3) Velocity (symbol = c): All forms of electromagnetic radiation

travel at the speed of light, c = 3 x 108 m/s

• The wavelength, frequency and velocity are related by the

expression:
c =λν
λ = c/ ν and ν = c/ λ
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 Properties of Emr waves Contd..
• Wave number ( symbol ῡ , pronounced as nu bar): This is the
reciprocal of the wavelength.

ῡ = 1/ λ = ν/c

• 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 λ = c/ ν
 For 1 GHz, λ = 3 x 108 m/s /1 x 109 s-1 = 0.3 m
100 GHz, λ = 3 x 108 m/s /100 x 109 s-1 = 3 mm
300 GHz, λ = 3 x 108 m/s /300 x 109 s-1 = 1 mm

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 c) Electromagnetic radiation spectrum
• Definition: This is the entire range of electromagnetic
radiations separated into different wavelengths or frequencies.

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 Visible Spectrum

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 d) Interaction of Emr with matter
• When an atom is bombarded by emr, it absorbs energy and
moves to an 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. E 1
E1
hv
hv

E0 E0
Energy is absorbed, absorption spectrum Energy is emitted, emission spectrum
produced produced
ΔE = E1 - E0 = hv ΔE = E1 - E0 = hv
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e) Calculation of energy associated with Emr
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 α ν or E = hν

Where h = Planck’s constant = 6.626 x 10-34 Js

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 Calculating energy associated with Emr …
3) The amount of energy emitted or absorbed by a body is in whole
number multiple of hν (or quantum)

E = nhν
Where n = 1, 2, 3 etc
• This is called quantisation of energy implying that energy occurs
in whole number multiples of hν

Example 2
• Calculate the energy of one mole of photons 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 Emr ...
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 = Avogadro’s 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, ῡ = 1/ λ = ν/c ; Hence E = hc ῡ = 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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 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
½ mv2). This can be represented as:

hv = hvo + ½ mv2
Photon energy Kinetic energy of an
Work function of
or incident energy emitted electron
A metal

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 Photoelectric effect ...
• Where , h = Planck’s 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
e- electrons
e-
e-
Ammeter to
e- e- measure current

Flow of electrons
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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 minimum 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
hv = h x c/λ = (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/Avogadro’s number
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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/λ we can determine λmax, i.e.

 3.837 x 10-19 J = (6.626 x 10-34 Js) x (3 x 108 m/s)
λ
 λ = (6.626 x 10-34 Js) x (3 x 108 m/s) /3.837 x 10-19 J
= 5.181 x 10-7 m
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 1.4 Bohr’s Atomic Model
• Niels Bohr developed the Bohr
model of the atom, in which he
proposed that:
1) An electron revolves round the
nucleus in fixed circular orbits
or shells called energy levels
 Electron in a particular shell is
associated with a certain amount
of energy.
 Energy increases with increasing
distance from nucleus.
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2) Electrons in stable orbits do not
radiate; on changing energy
levels, radiation equivalent to
the energy difference between
the levels is involved.
 ΔE = E2 – E1 = hν = hc/λ
 they change orbits by absorbing
or emitting photons
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 Bohr’s Atomic Model Contd.
3) Electron can only move in the h = Planck’s constant = 6.626 x 10-34
orbits in which the angular Js
momentum (mvr ) of the n = an integral number which
revolving electron is an integral denotes the number of orbit.
multiple of h/2π
• The equation mvr = nh/2 π means
that the angular momentum of the
 mvr = nh/2 π
revolving electron is quantised which
implies that the magnitude of the
where, angular momentum is always a whole
m = mass of electron = 9.108 x 10-31 kg number not fraction.
v = velocity of electron
r = radius of the orbit in which
electron is revolving

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 The Hydrogen Atom According to Bohr

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 Bohr’s Atomic Model Contd.
• Assuming coulombic interaction and the applicability of
Newtonian mechanics, the following values may be
directly obtained for the hydrogen atom

 The radius of an electron orbit (spherical) in hydrogen is given

by:

 It can be seen that the smallest electron orbit in hydrogen is given

for n = 1 at ro = 0.529 Å. It is also seen that r increases with n2 (r =
n2ro)
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 Bohr’s Atomic Model Contd...

 The energy of an orbiting electron characterized by the

principal quantum number (n) is given as:

 This relationship indicates that electron orbits with increasing

principal quantum number (n) assume decreasing negative values
(1/n2) with the limiting value (n → ∞) being zero.

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 Bohr’s Atomic Model Contd.
 For convenience, it is frequently customary to express
electronic energies in terms of wave numbers (ῡ) with the
units of [m–1].

 This conversion may bereadily made since E = hν. Hence

 Upon substituting the numerical values for all the constants,

we obtain:

 where n = 1, 2, 3, 4, etc. The value of 10973500 is referred to as the Rydberg

constant (R; also RH)
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 Bohr’s Atomic Model Contd.
• The energy changes associated with electronic transitions and
the accompanying emission or absorption of radiation may
simply be calculated as follows:

• In terms of ῡ, we obtain for emission of radiation:

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 Bohr’s Atomic Model Contd.
Or

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 Atomic Spectra in a Hydrogen Atom
• Atomic spectra constitute the frequencies / wavelengths of light
emitted or absorbed by a given atom.

• The absorption and emission of light by hydrogen atoms thus

correspond to energy changes within its atoms.

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 Exercise
1.

2.

3.

4.

5.

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 Bohr’s Atomic model
A : Achievements B: Limitations
1) Explained the 1) It does not explain the origin of spectra
stability of atom given by multi-electron species.
2) Explained how 2) It assumes the circular orbits in which the
emission spectrum is electrons revolve are planar instead of 3
produced dimensional.
3) Explained how 3) It does not explain the cause of Zeeman
absorption spectrum and Stark effects:
is produced 1) Zeeman effects- splitting of spectral lines in
magnetic field
4) Explained the origin
2) Stark effect - splitting of spectral lines in
of spectral lines in electric field
hydrogen spectrum
4) It does not account for uncertainty
eg. Lyman, Balmer,
principle and dual nature of electrons.
Paschen, Bracket
and Pfund series 5) It does not explain the origin of fine
structures observed in the spectral lines
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using high resolution microscope.
Wave Function Concepts of Atomic structure

1) De Broglie’s wave Equation

• Just like Emr can behave both as a wave and as particles, in the
same manner, electrons, protons and neutrons which are
particles can also behave as waves. Hence, when in motion, they
possess properties such as wavelength (λ), amplitude (A), and
frequency (v ).

Diffraction of waves
by aluminum;
(a) X-rays of
wavelength 0.71Å
(b) Electrons of
wavelength 0.50Å

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 De Broglie’s wave equation Contd.

• Louis de Broglie proposed in 1924, that electrons are particles

in the real sense but they also exhibit a wavelike behavior

• He derived an expression describing the relationship between

the wavelength associated with the mass m of a body moving
with velocity v.

Given Planck’s quantum theory Ephoton = h

 If the photon has a mass m, therefore using the Einstein

equation, E = mc2, we may equate the energy of the photon
with the relativistic energy of a particle,
Ephoton = mc2 = h
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 De Broglie’s wave equation Contd.

mc2 = hv = hc/λ
mc = h/ λ
λ = h/mc = h/p
where p = momentum of the particle.

 This implies that all particles in motion have a wavelength

that depends on the particle’s momentum.

 The larger the momentum of the photon the shorter the

wavelength it exhibits, hence more energetic.

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 Example:
• 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) λ = 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, λ = 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

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2) Heisenberg’s Principle of Uncertainty
• The wavelike behavior of electrons brought about limitations of
determining the path that an electron will take around the nucleus
in an atom as Bohr had suggested.

• This implies that if an electron behaves as a wave, then it will not

be in existence in a particular location as a point.

e- changes momentum at
the instant of collusion Photon
Expected path of the electron
e-
Momentum of e- changes when
a photon of light strikes it.
+

16/02/2018 Nucleus 40
 Heisenberg’s Principle of Uncertainty Contd.

 If momentum or velocity of the particle is accurately determined, the

measurement of position will be less precise.

 Heisenberg’s Uncertainty Principle therefore states that ‘it is

inherently impossible to know both the exact energy (momentum)
of the electron and its location in space’

 i.e. you cannot know precisely the location and the speed of an
electron in a given atom simultaneously

 This disapproved Bohr’s theory, of imagining electrons as points,

moving in well-defined orbits about the nucleus always at the same
radius. Bohr’s theory was based on classical mechanics concept.
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 Heisenberg’s Uncertainty Principle contd.
• We must therefore use quantum mechanics, so that if we think
of the electron as a particle, we talk of the probability that the
electron will be found at some particular location in the atom.

• E.g. In a hydrogen atom in its ground state where its electron is

in the lowest energy level, the probability of finding the electron
is greatest at a distance close to the nucleus and then decreases
with increasing distance from this given distance (point).

• Therefore there is a 90% probability of finding the electron

somewhere inside, a spherical surface of radius ‘r’ which is 1.4 x
10-10m in the hydrogen atom and only 10% probability of finding
the electron at a greater distance beyond ‘r’.

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 Heisenberg’s Uncertainty Principle contd.
 We call these descriptions of the electrons probable location
as probability distribution.

 Electrons are thus seen not as a point, but as a spread–out

cloud of negative charge that is most dense near the nucleus
and less dense further away.

 This density distribution is known as the electron density

distribution.
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 Heisenberg’s Uncertainty Principle contd.
 Although the Uncertainty Principle is valid for all particles, only
submicroscopic particles which are small enough and have small
enough momentum will exhibit uncertainty quantities that have
significant magnitudes relative to their quantities being measured.

• Heisenberg suggested that, if a position measurement is made with

an uncertainty ∆x and a momentum measurement is simultaneously
made with an uncertainty ∆p, then the product of the two
uncertainties is equal or greater than the Planck’s constant h.

∆x∆p≥h

 This puts a limit to large particles implying that they will not exhibit
the principle explicitly. Hence only submicroscopic particles, such as
electrons and photons will exhibit wave-like characteristics 44
 3) Schr’o’dinger’s Wave Equation
• This is based on the assumption that if electron behaves like a
wave, there must be a wave equation describing its motion.

• Schr’o’dinger’s equation describes the position of electron in

three dimensional space around the nucleus.

• If we represent a wave by the sine function, then,

Ψ = A sin (2πx/λ)

where A = amplitude of the wave, x = displacement from the origin,

λ = wavelength of the wave.

• Differentiating the wave equation twice with respect to (wrt) x,

45
 Schr’o’dinger’s Wave Equation cont.
• δΨ/δx = A(2π/λ) cos (2πx/λ)

• δ2Ψ/δx2 = (-4π2/λ2)A sin(2πx/λ) = - (4π2/λ2) Ψ

• Noting that total Energy E = PE + KE = V + ½mv2

=> 2E = 2V +mv2

• Making v2 the subject,

=> V2 = 2(E – V)/m

 From De Broglie’s equation,

λ = h/mv = λ2 = h2/m2v2
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 Schr’o’dinger’s Wave Equation contd.
• Substituting for v2,
 λ2 = {h2/m2} x m/2(E-V) = h2/2m(E-V)

• Substituting for λ2

 δ2Ψ/δx2 = - (4π2/λ2) Ψ = - {4π2 x 2m(E-V) / h2} Ψ

δ2Ψ/δx2 + 8π2 m(E-V)/h2) Ψ = 0

 This is the wave equation for a particle moving along the x -

axis.

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 Schr’o’dinger’s Wave Equation contd.
• For 3 dimensional space,

 δ2Ψ/δx2 + δ2Ψ/δy2 + δ2Ψ/δz2 + 8π2 m(E-V)/h2)Ψ = 0

 This is the Schr’o’dinger’s equation

 The equation can be further reduced to,

  2 Ψ + 8π2m (E-V) Ψ = 0
h2

Where,  2 = δ2/δx2 + δ2/δy2 + δ2/δz2 and is called the Laplacian

operator
48
 Schr’o’dinger’s Wave Equation cont.
• This equation may be rearranged into,

(V- 2h2) Ψ = E Ψ
8π2m

=> H Ψ = E Ψ

• Where H = V -  2h2/8π2m 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 Ψ is called Eigen function.
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 Significance of the wave function (Ψ)

• The wave function Ψ (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 (Ψ2) is always positive, hence gives the
probability of finding an electron around the nucleus.

50
 Schr’o’dinger’s Wave Equation contd.

• Solving the Schr’o’dinger equation for each electron (1, 2,

3 etc) gives the shape of an atomic orbital, which is defined
as the three dimensional space in which the probability of
finding electron is maximum.

• To each solution or orbital there corresponds a certain value

E1, E2, E3 etc of the total energy of the system.

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 Differences between an orbit and atomic orbital
Orbit
1. Is a definite circular path at a fixed
distance from the nucleus in which electron
revolves
2. It indicates the exact position of an
electron in an atom
3. There is certainty about movement of
electron in an orbit
4. It represents planar motion of electron
5. Maximum number of electrons in orbit =
2n2 where n = number of orbit
6. Orbits are circular in shape
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Atomic orbital
1. A 3 dimensional region or space around
the nucleus within which the probability of
finding electron with a definite energy is
maximum.
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. No certainty about movement of an
electron in an orbital
It represents 3 dimensional motion of
electron
5. Maximum number of electrons in an
orbital = 2, the two must have opposite
spins
6. Orbitals have different shapes e.g. S-
orbitals are spherical, p-orbitals are egg
52
shaped etc.
 Quantum numbers
• These are integral numbers that describe:
1) The energy of electron in an orbit,
2) The position of electron from the nucleus
3) Shape and the number of orientations of orbital round its own axis
4) Orientation of the spinning of electron round its own axis

• There are four types of quantum number i.e.

1) The principal quantum number (n)
2) Azumuthal quantum number (l)
3) Magnetic quantum number (m)
4) Spin quantum number (s)

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 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

3) It gives the energy (E) of an electron in an orbit

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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 Azimuthal Quantum Number (l)

• It determines the magnitude of the orbital angular momentum

hence also called orbital angular momentum quantum number.

• It is disgnated by l

• It assumes values from 0, 1, 2 ... (n-1)

• The values of l represent a particular sub-shell within the principal

shell i.e.

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 Azimuthal Quantum Number (l) contd.
For example:
• 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.
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 Azimuthal Quantum Number (l) contd.

• The maximum number of electrons that can be accommodated

in a given subshell = 2(2l +1)

• Example:

Orbital Value of l 2(2l +1)

s 0 2

p 1 6

d 2 10

f 3 14

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 Magnetic 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 sub-

shell.

• It takes values from –l, 0, +l

• E.g.:
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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 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 (+ ½ ) or ( ) or (α spin)
2) Anticlockwise (- ½) or ( ) or (β spin)
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 Relationship between quantum numbers
Principal Values of l Total Different Max Max
Quantum and number Number of values of m number of number of
number (n) of sub-shells electrons in electrons in electrons in
a sub-shell = orbital = 2 x main shell =
2(2l+1) number of 2n2
orbitals
1 0 2 (2x0 +1) = 0 2x1=2 2 x 12 = 2
(s -sub-shell) 2
2 0 2 (2x0 +1) = 0 2 x 1= 2
(2s orbital) 2 2 x 22 = 8
1 (2 p- 2(2 x 1+1) = -1; 0; +1 2x3=6
orbital) 6
3 0 (3 s- 2(2x0+1) = 2 0 2x1=2
orbital)
1 (3 p- 2(2x1+1) = 6 -1; 0; +1 2x3=6 2 x 32 + 18
orbital)
2 (3 d- 2(2x2+1) = -2; -1; 0; +1; 2 x 5 = 10
orbital) 10 +2
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 Types of atomic orbitals
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

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 p - Orbitals
• There are three p-orbitals px, py, and pz
• They lie along the x-, y- and z- axes of a Cartesian system.
• Each has two egg shaped lobes on each side of the nucleus
• The orbitals are degenerate
• 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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 d - Orbitals
• 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 z-axes, the
remaining two lie in a
plane aligned along the x-,
y- and z-axes.

63
 f - Orbitals
• There 7 types of f-orbitals

16/02/2018 64
 Electron configuration
• This is the distribution of electrons into different atomic orbitals in
order of increasing energy levels. It shows in which orbitals
electrons are located.

• The filling of atomic orbitals follow 3 principles:

1) Pauli’s exclusion principle
2) Aufbau’s principle
3) Hund’s rule of maximum multiplicity

1) Paul’s 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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Electron Spin and the Pauli
Exclusion Principle

Since electron spin is quantized, we

define ms = spin quantum number = 
½.

Two electrons in the same orbital

must have opposite spins.

S = -1/2 S = +1/2
66
 Paul’s exclusion principle cont.
Main Combin Different Values of n, l, m, Electron Total Total
shell (n) ation and s with upward number of number of
number and electrons in electrons in
downward orbital main shell
arrows

1 1 N = 1; l= 0; m= 0; s= +1/2 ↑ 2 (1s2) (↑↓) 2 x 12 = 2

2 N = 1; l = 0; m = 0; s = -1/2 ↓
2 1 N = 2; l= 0; m= 0; s= +1/2 ↑ 2 (2s2) (↑↓) 2x22 = 8
2 N = 2; l = 0; m = 0; s = -1/2 ↓
3 N = 2; l = 1; m = 0; s = +1/2 ↑ 2 (2pz2)
(↑↓)
4 N = 2; l = 1; m = 0; s = -1/2 ↓
5 N = 2; l = 1; m = +1; s = +1/2 ↑ 2 (2py2)
(↑↓)
6 N = 2; l = 1; m = +1; s = -1/2 ↓
7 N = 2; l = 1; m = -1; s = +1/2 ↑ 2 (2px2)
(↑↓)
8 N = 2; l = 1; m = -1; s = -1/2 ↓
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 Aufbau Principle
• Also referred to as the building up principle

• It states that, electrons orbiting one or more atoms fill the

lowest available energy levels before filling higher levels (e.g.,
1s before 2s).

• 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 < 2p

2) Orbitals having similar (n + l) values, the orbital with lower

value of n will have lower energy e.g. 3p < 4s
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 Orbitals in Many Electron Atoms
Order of filling atomic orbitals
• Energy levels of orbitals

69
 Hund’s 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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Short form of electron configurations
• For shorthand electron • For atoms having p, d and f
configurations orbitals, the most stable
– Write the core electrons electron configuration is when
corresponding to the filled the d and f orbitals are half or
Noble gas in square brackets. fully filled.
– Write the valence electrons
explicitly. • Example:
• Example, • Cu (Z = 29)
• P: 1s22s22p63s23p3 but Ne is Stable ec: = 1s2, 2s2, 2p6, 3s2,
1s22s22p6 3p6, 4s1, 3d10
• Therefore, P: [Ne]3s23p3.
• Cr (Z = 24)
Stable ec: = 1s2, 2s2, 2p6, 3s2,
3p6, 4s1 3d5
71
 Effective Nuclear Charge
• Effective nuclear charge: is the net charge experienced by an
electron in a multi-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 multi-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 (σ)

Z eff = Z - σ
72
 Screening and Penetration

• Electrons near the nucleus shield from the nuclear charge,

those electrons which are further away.

• This effect, known as shielding, decreases Zeff experienced

by the valence electrons.

• The extent to which an electron in an orbital is shielded by the

electrons in other orbitals depends upon the extent to which it
penetrates the core electron cloud around the nucleus.

• The more penetrating an orbital, the closer the electrons can,

on average, get to the nucleus, and the higher the value of
Zeff they experience. 73
 Screening and Penetration

• The shielding and penetration effects are apparent in the way the
relative energies of the orbitals in atoms vary with increasing atomic
number.
• E.g. s orbital penetrates more than the p orbital, hence an s electron
experiences a higher Zeff and has a lower energy. As the atomic
number, Z, increases, the added core s and p electrons shield the
outermost electrons, reducing the rate at which the Zeff they
experience increases. 74
Electron Configurations and the Periodic
Table

75
 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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 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 2
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electrons
 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

1) They often form coloured compounds
2) They can have a variety of different oxidation states
3) They are often good catalysts e.g. Mn, Fe, Co, Cr
4) They are silvery-blue at room temperature (except Cu and Au)
5) They are solids at room temperature (except mercury)
6) They form complexes
7) They are often paramagnetic.

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 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
• Welder’s goggles
• TV and Computer monitors
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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.
79
 Atomic properties

• These are properties that change from one

element to the other, hence used to
characterise elements
1) Atomic radius
2) Ionization energy
3) Electronegativity
4) Electron affinity
5) Magnetic properties
6) Acidity and alkalinity of oxides
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 1. 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.

81
 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.
82
Variation of I1 as Z Varies

Period Table 83
The In of Group n

Period Table 84
 2. Atomic & Ionic radii

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Atomic radii as Z increases
 Atomic radius
decreases across
the period

 Atomic radius
increases down the
group

Period Table 86
 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– F– Ne
Na+ Mg2+ P3– S2– Cl – Ar
K+ Ca2+ Se2– Br – Kr
Rb+ Sr2+ Te2– I– Xe
Cs+ Ba2+
Period Table 87
 3. 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.

88
Note the relationship of EAs and Is.
 4. 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
electronegative atom, hence the bond is polarised

+ – 0 0

H Cl H H
 Electronegativity contd.

What trends do
you observe:

1. Across the
period?

2. Down the
group?

Explain your
answer

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 5. Magnetic Properties
• Materials can be divided into three types according to
their magnetic properties.
• 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 91
 6. Oxides

I: Oxides of non-metals I: Oxides of metals

 Are acidic  Are alkaline

 Strong acids e.g.  Strong bases e.g.
H2SO4, HNO3, NaOH, KOH,
HClO3, HClO4 Ca(OH)2

 Weak acids .g.

H2SO3, H2CO3,
HNO2, HClO2,

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