CHEM 151: BASIC INORGANIC

CHEMISTRY
LECTURE 1
 COURSE OUTLINE
• Atomic structure; qualitative wave mechanics
• Periodic table and periodicity, reactive
parameters
• Chemical bonding
– Molecular,
– ionic
– Covalent
– Metallic
– Van der waal’s bonding

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 COURSE OUTLINE
• Forces within molecules
– Bond strength
– Bond energy
– Polarity
– Continuity of bonds
• Valence bond theory, resonance, multiple bond,
shapes of molecules, hybridization of non-
transition elements
• Crystal structures
• The principal types of unit cell space lattice

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 QUIZES AND EXAMINATIONS
• 1st Quiz:
Form of exam: Written (30 marks)
• Mid-semester:
Form of exam: Written (30 marks)
• End of Semester:
Form of exam: Multiple choice (100 marks)

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 ATOMIC STRUCTURE
Atom : An atom is the smallest particle of an
element that retains the properties of that
element.
• Original ideas on atomic structure consisted of a
positively charged ‘cloud’ with embedded,
negatively charged, particle-like electrons.
• This was superseded by the Rutherford’s model in
which a central, positively charged nucleus,
containing most of the mass of the atom, was
surrounded or orbited by the much lighter
electrons.
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 ATOMIC STRUCTURE
• The atom was viewed as a miniature solar
system in which the nucleus was analogous to
the sun and the electrons to the planets but
this was a simple model.
• It was inconsistent with classical physics which
predicted that the electrons in such an atom
should spiral into the nucleus with
concomitant emission of radiation.

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 ATOMIC STRUCTURE
• Observations in atomic spectroscopy showed
that the electrons could have only certain
orbits or energies.
• This observation provided a way around the
problem but from a theoretical standpoint,
this factor had to be introduced on a purely
adhoc basis with no clear idea of why it should
be so.
• The resulting picture formed the basis of the
subsequent model proposed by Niels Bohr.
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 ATOMIC STRUCTURE
• This model was quite successful in explaining
the observed spectroscopic properties of the
hydrogen atom, the simplest of all atoms
containing only a single electron.

• The model soon ran into problems with

heavier atoms containing more than one
electron.

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 ATOMIC STRUCTURE
• The French scientist Louis de Broglie had the
curious idea that the same wave-particle
duality, or combined wavelike and particle-like
character, should apply to matter too.
• In 1924, he suggested that we should also
think of an electron as having the properties
of a wave.

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 ATOMIC STRUCTURE
• He proposed that every particle has wavelike
properties, including a wavelength that is
related to its mass m and speed υ by the De
Broglie relation

λ=

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 ATOMIC STRUCTURE
• According to this relation, a heavy particle
travelling at high speed has a small wavelength λ.
• A small particle travelling at low speed has a large
wavelength.
• Because of its wavelike character, we cannot say
precisely where an electron is when it is travelling
along a path.
• This is expressed numerically by the uncertainty
principle discovered by Werner Heisenberg.
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 ATOMIC STRUCTURE
• Heisenberg found that the more precisely we
know the position of a particle, the less we can
say about its speed, and vice versa.
• More specifically, if we know the position of a
particle of mass m to be within a range Δx, then
its speed must be uncertain by at least an
amount Δυ, where

ℎ
Δx× (m× ∆𝜐)≥
4𝜋

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 ATOMIC STRUCTURE
• If Δx is zero (meaning we have perfect knowledge
about the location), the only way this inequality
can be satisfied is for Δν to be infinite (meaning
we are totally ignorant about the speed).
• Similarly, if the speed is certain (Δν is zero), the
position must be completely uncertain (Δx is
infinite).
• The uncertainty principle implies that Bohr’s
picture of electrons travelling in precise orbits
cannot be valid, because an electron in such an
orbit has a definite position and definite speed at
every instant.
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 ATOMIC STRUCTURE
• An elegant solution to the problem was provided
by Schrödinger in 1926.
• He proposed the electrons in atoms should be
considered not as particles but as waves and that
they could therefore be described by a suitable
wave equation.
• The important conceptual breakthrough here was
that the presence of only certain allowed
electron energies is a direct and natural
consequence of a wave treatment and no ad hoc
assumptions are necessary.
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 ATOMIC STRUCTURE
• The Schrödinger wave equation is used to describe the
behavior of electrons in atoms,
– i.e. we treat electrons as waves such that only certain
solutions to the wave equation, or energies for the
electron, are possible and this quantization results directly
from boundary conditions.
• Moreover, we obtain not one solution but a series of
many possible solutions each with certain energy and
each described by a certain set of quantum numbers.
• Each one of these solutions or wavefunctions (ψ)
describes a possible state of the electron in the atom
and this is called an orbital.
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 ATOMIC STRUCTURE
• The solutions or wavefunctions, ψ, refer to the
amplitude of an electron wave.
• Of more physical significance is the square of
this function (ψ2) which refers to the electron
intensity (density) or more precisely a
probability of finding an electron.

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 ATOMIC STRUCTURE
• Thus ψ2 at any particular point is the
probability of finding the electron at that
point.
• High values of ψ2 mean high probability, low
values mean low probability;
• ψ2 equal to zero means zero probability.

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 Quantum Numbers
• Boundary conditions and the spherical, three-
dimensional nature of the atom give rise to
three quantum numbers and these are given
the symbols n, l and ml.
• These can take only certain allowed values
and a solution exists to the Schrödinger
equation for certain allowed sets of these
three numbers.

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 Quantum Numbers
• The names and symbols for these quantum numbers
and the values which they can take are given below as
follows:

– n is the principal quantum number and this determines the

radial part of the wavefunction. The energy of the orbital
also depends on n but not on l and ml. The number n can
take integral values 1, 2, 3, 4….∞ but we will be concerned
only with the first few.
– l is the subsidiary or angular momentum quantum number.
This determines the shape of the orbital and can take
values 0,1, 2, 3…n-1, i.e. the possible values of l are
dependent on n. In fact, l determines the type or shape of
the orbital and these are usually referred to by letters.
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 Quantum Numbers

• l=0 s orbital
• l=1 p orbital
• l=2 d orbital
• l=3 f orbital

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 Quantum Numbers
• Orbital are then labeled according to their value of
n and the letter associated with l:

• n=1 l=0 1s
• n=2 l=0 2s
• n=2 l=1 2p
• n=3 l=0 3s
• n=3 l=1 3p
• n=3 l=2 3d
Note that orbitals such as 1p and 2d are not allowed
according to these rules.
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 Quantum Numbers
• ml is the magnetic quantum number and it takes
values -l, -l+1,…0…, l-1, l, i.e. 2l+1 values for a given
value of l.
• Thus for l=0, ml =0 and so there is only one type of
s orbital for any given value of n, i.e. one 1s, one 2s
etc.
• For l=1, ml=-1, 0, +1, i.e. three types of p orbital;
three 2p, three 3p etc.
• For l=2, ml=-2, -1, 0, +1, +2, i.e. five types of d
orbital.
• This quantum number specifies the orientation of
the orbital.
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 Quantum Numbers
• When we look at these orbitals or wave
functions in more detail we will see that they
contain nodes and there are a few simple rules
concerning nodes that are worth remembering.
• The total number of nodes in any orbital is
given by n-1.
• Some of these are in the radial part of the wave
function and some are in the angular part.

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 Quantum Numbers
• In the case of the hydrogen atom, the energy of an
electron or orbital depends only on the value of n
and so, for example, the 2s and 2p orbitals have
the same energy and are said to be degenerate.
• The energy of the orbitals increases as n increases.
The separation in energy is not constant but that
the levels become closer together as n increases.
Moreover, the energies are given negative values
with n=∞ defined as zero energy.

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The angular part of the wavefunction
• The angular part of the wavefunction reveals how the
wavefunction varies as a function of angle from the
origin of some suitably chosen coordinate systems and
thus determines the shape of the orbital.
• It is dependent on the quantum number l and we can
label the types of orbitals according to this quantum
number or more usually with the letters s, p, d, f, etc.
• The number of nodes in the angular part of the
wavefunction for a given orbital is equal to l.
• Thus, s orbitals (l = 0) have no angular nodes. Moreover,
since there is no angular dependence, the orbital is
spherical and this is true for all s orbitals; 1s, 2s, 3s, etc.
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The angular part of the wavefunction
• For p orbitals, l=1 and there is one angular node.
• This is planar and divides the orbital into two lobes
of opposite sign.
• There are three possible orientations for orbitals of
this type (three values of ml) which lie along the
axes x, y and z, and these are usually designated as
px, py and pz.
• All p orbitals have this shape and there are always
three for any given value of n, i.e. three 2p, three
3p etc.
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The angular part of the wavefunction
• For d orbitals, l=2 and there are therefore two nodes
associated with these orbitals.
• These are perpendicular and each orbital has four lobes.
• There are five d orbitals which are given the labels dxy,
dxz, dyz, dx2-y2 and dz2.

Figure: diagrams of angular part of the wavefunction for selected orbitals

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 The radial part of the wavefunction

• The radial part of the wavefunction tells us

how the wavefunction varies with distance, r,
from the nucleus, i.e. the effective size of the
orbital.
• Atomic orbitals depend on an exponential
function 𝑒 −𝐵𝑟 where B is some constant and r
is the distance from the nucleus.
• This means that ψ falls away exponentially at
large r values.

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 The radial part of the wavefunction

• For a 1s orbital, a standard expression is

ψ=A𝑒 −𝐵𝑟 and if we plot this function as a graph,
we obtain a curve shown in figure below.
• We can see that there is a maximum value of ψ at
r = 0 or at the nucleus.

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 The radial part of the wavefunction

• The probability of finding an electron on a

particular surface rather than at a point along
a line from the nucleus is of interest at this
stage.
• Considering the 1s orbital, we can imagine a
spherical surface expanding from the nucleus
and it will be useful to know the probability of
finding an electron at some point on this
surface as a function of distance from the
nucleus.
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 The radial part of the wavefunction

• The greater the distance from the nucleus, the

more points on a sphere and so the function
we want will be proportional to the surface
area of the sphere or 4𝜋𝑟 2 .
• We can therefore plot a probability that an
electron is at a certain distance r according to
the function 4𝜋𝑟 2 . 𝜓 2 .
• This is called the radial probability function
(RPF).
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 The radial part of the wavefunction

• The graphs of RPFs of 1s, 2s, 2p, 3s, 3p and 3d

orbitals are shown in Figure 2.
• When r = 0, the RPF is also 0 and so for all
orbitals, the function is zero at the centre of
the nucleus.
• The graph has a maximum, i.e. there is a
distance at which we are most likely to find an
electron, ro.

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The radial part of the wavefunction

Figure 2 Graphs of RPFs of 1s, 2s, 2p, 3s, 3p and 3d orbitals

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