Atomic number and mass number


Atomic number(Z)
=number of protons present in the nucleus
= number of electrons in the neutral atom.

Electrons and protons together in a nucleus
are called nucleons.

Mass number (A)
= number of protons (z) +
number of neutrons(n)
1
 Quantum Numbers


Principal quantum number, n (n = 1, 2, 3, 4, 5, …)


Secondary (azimuthal) quantum number(l)

 Magnetic quantum number, (ms)


Spin quantum no.(s)

2
 Principal quantum number

The principal quantum number, n, defines the shell in which a
particular orbital is found.

n must be a positive integer

n = 1 is the first shell, n = 2 is the second shell, etc.

Each shell has different energies.

The principal quantum number determines the size and to large extent
the energy of the orbital. Size of an orbital increases with increase of
principal quantum number ‘n’. In other words the electron will be
located away from the nucleus. Since energy is required in shifting away
the negatively charged electron from the positively charged nucleus, the
energy of the orbital will increase with increase of n.
3
 Azimuthal quantum number

It defines the three-dimensional shape of the orbital.

For a given value of n, l can have n values ranging from 0 to n
– 1, that is, for a given value of n,
the possible value of l are : l = 0, 1, 2, ..........(n–1)
For example, when n = 1, value of l is only 0.
For n = 2, the possible value of l can be 0 and 1.
For n = 3, the possible l values are 0, 1 and 2.

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
Each shell consists of one or more subshells or sub-levels. The
number of sub-shells in a principal shell is equal to the value.

For example in the first shell (n = 1), there is only one sub-shell which
corresponds to l = 0.

There are two sub-shells (l = 0, 1) in the second shell (n = 2), three (l
= 0, 1, 2) in third shell (n = 3) and so on. Each sub-shell is assigned an
azimuthal quantum number (l). Sub-shells corresponding to different
values of l are represented by the following symbols.

Value for l : 0 1 2 3 4 5 ............
notation for s p d f g h ............ sub-shell

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6
 Magnetic quantum Number

The third quantum number is the magnetic
quantum number, m is dependent on l values.


m has integer values.


m may be either positive or negative.


m’s absolute value must be less than or equal to l.


For l = 1, m = -1, 0, +1

7
 Spin quantum number

The electron spins on its own axis and
have angular momentum that
represents two orientation or spins: ½
and -½


It is represented by two arrows ↑ and ↓
showing that these have opposite spins.

8
How are the quantum numbers related?
10
 Boundary
surface diagrams
of orbitals

11

In the boundary surface diagrams the nucleus is
taken to be at the origin.

S-orbital is spherical.

p-orbital consists of two sections called lobes that
are on either sides of the plane where the two
lobes touch each other. The size, shape and
energy of the three p-orbitals are identical.

Since the lobes are considered along the x, y and
the z axis they are designated as:-
px, py, pz

It should be understood that there is no relation
between magnetic quantum number and x, y, z
directions. 12
Boundary surface diagrams for 2p orbitals

13
 d- orbitals

The 5 d-orbitals are designated as:-

 The shapes of the first four d-orbitals are similar to

each other, whereas the fifth is different from the
others.
 All the five d- orbitals and are equivalent in energy.
 The d- orbitals for which n > 3 also have shapes similar
to 3d orbital, but differ in energy.
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15
 Aufbau principle

Aufbau principle deals with filling up of electrons.
“In the ground state of the atoms , the orbitals
are filled in order of the increasing energies.”

In other words, electrons first occupy the lowest
energy orbitals available to them and then enter
higher energy orbitals after lower energy orbitals
are filled.

Order of increasing order of energies in the
orbital is as follows:- 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p,
5s, 4d, 5p, 4f, 5d, 6p, 7s…….. 16
Order of filling

up of electrons

17
1. Using s, p, d and f notation, describe the
orbital with the following quantum numbers:

(a) n = 1, l = 0 (b) n = 3, l
=1

(c) n = 4, l = 2 (d) n = 4, l
=3

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2. How many electrons in an atom have the
following quantum numbers?
a. n = 4, ms = -1/2 b. n = 3 , l =
0

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20
21
22
3. Explain, giving reasons, which of the following
sets of quantum numbers are not possible.
(a) n = 0, l = 0; ml = 0, ms = + ½

(b) n =1, l = 0; ml = 0, ms = - ½

(c) n =1, l = 1; ml =- 0, ms = + ½

(d) n = 2, l = 1; ml = 0, ms = + ½
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4. (a) What is the lowest value of n that allows g orbitals

to exist?
(b) An electron is in one of the 3d orbitals, Give the
possible values of n, l and ml for this electron.

24
5. Write down the quantum numbers n and l
for the following orbitals:
a) 2p b) 3d c) 5f

25
6. (a)The quantum numbers of six electrons are given below.
Arrange them in order of increasing energies. Do any of these
combination(s) have the same energy lists:
1. n= 4, l = 2, ml = –2, ms= –1/2
2. n= 3, l = 2, ml = 1, ms= +1/2
3. n= 4, l = 1, ml = 0, ms= +1/2

4. n = 3, l = 2, ml = –2, ms= –1/2

5. n = 3, l = 1, ml = –1, ms= +1/2
6. n = 4, l = 1, ml = 0, ms= +1/2

26
7. (i) The unpaired electrons in Al and Si are present in 3p
orbital. Which electrons will experience more effective
nuclear charge from the nucleus?

(ii) Indicate the number of unpaired electrons in:

(a) P (b) Si (c) Cr (d) Fe

27
Give the name and atomic number of the inert gas
atom in which the total number of d-electrons is equal
to the difference between the numbers of total “p” and
total “s” electrons.

28
Which of the following options does not represent
ground state electronic configuration of an atom?
(i) 1s2 2s2 2p6 3s2 3p6 3d8 4s2
(ii) 1s2 2s2 2p6 3s2 3p6 3d9 4s2
(iii) 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(iv) 1s2 2s2 2p6 3s2 3p6 3d5 4s1

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Which of the following is responsible to rule out the existence of
definite paths or trajectories of electrons?
(i) Pauli’s exclusion principle.
(ii)Heisenberg’s uncertainty principle.
(iii)Hund’s rule of maximum multiplicity.
(iv)Aufbau principle.

30
31
32
33
 Schrodinger wave equation
Schrödinger Equation is a mathematical expression which describes the
change of a physical quantity over time in which the quantum effects like
wave-particle duality are significant. The Schrödinger Equation has two
forms: the time-dependent Schrödinger Equation and the time-independent
Schrödinger Equation.

34
 Significance of ψ and ψ 2

• ψ is a wave function and refers to the amplitude of electron

wave, i.e. probability amplitude. It has got no physical significance.
The wave function ψ may be positive, negative or imaginary.
• Wave Function, in quantum mechanics, is a variable quantity that
mathematically describes the wave characteristics of a particle. The
value of the wave function of a particle at a given point of space and
time is related to the likelihood of the particle's being there at the
time.
• [ψ]2 is known as probability density and determines the
probability of finding an electron at a point within the atom.
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36
 Pauli’s exclusion principle

Consider two electrons in atom present in the same 1s orbital. The values for the four
quantum numbers is as follows:


Electron – 1


Electron - 2

Even if the values of 3 quantum numbers are the same, the value of 4th quantum number
is different. 37
 Hund’s rule of maximum multiplicity

This rule deals filling of electrons in the orbitals
belonging to the same subshells of equal energy
called degenerate orbitals.

It states that pairing of electrons in the
orbitals belonging to the same sub shell (p,d,
or f) does not take place until each orbital of
that sub shell gets one electron, i.e. singly
occupied.

Some of the orbitals acquire extra stability due to
their symmetry. 38
39
 Why is the energy of an electron negative?

The negative sign means that the energy of the electron in
the atom is lower than the energy of a free electron at rest.

A free electron at rest means that is infinitely far away from
the nucleus and has the negligible attraction towards the
nucleus. Thus it is assigned the energy value of zero. E ∞ = 0.
 As the electron gets closer to the nucleus En becomes larger
in absolute value and more and more negative..

40
 Electronic configuration

The distribution of electrons into orbitals of an
atom is called its electronic configuration.

Electronic configuration can be represented in
two ways:-
(a)Normal notation and
(b) orbital diagram
As given in the textbook.
The electron in the completely filled electronic shell
with the highest principal quantum number are
called valence electrons. 41
Electronic configuration of Cr(At.no. = 24):

 1s2 2s2 2p6 3s2 3p6 4s2 3d4


Electronic configuration of Mn(atomic number 25):

42
 STABILITY OF FULLY-FILLED AND HALF-FILLED
ORBITALS
The stability of half-filled and completely filled electronic configurations is due to
the following:
(i) Stability based on symmetry:
The expected electronic configuration of Cr (Z = 24) is:

43
(ii) Stability due to exchange energy:
If the electronic configuration of Cr is 3d44s2, then the electron in d-subshell can exchange in the
following ways:


The first electron (number 1) can exchange its potions with electrons numbered 2, 3 and 4.
i.e., in 3 ways.

The second electron can exchange its positions in two ways with electrons 3 and 4 only because
the exchange of position between 1 and 2 has already been considered in step (i).

The electron (number 3) can exchange only in one way. i.e., with electron 4.

44
45
Why does 3d orbital have more energy than 4s orbital?

According to (n + l) rule,
For 3d- orbital, n = 3 and l = 2.
Hence, n + l = 3 + 2 = 5

For 4s orbital, n = 4 and l = 0.

Hence, n + l = 4 + 0 = 4

Since (n + l) is greater for 3d orbital than 4s orbital, 3d orbital is of

greater energy than 4s.
46
 De Broglie’s relationship
According to Einstein’s mass energy relationship, E = mc 2
According to Planck’s statement, E = hν

mc2 = hν
mc2 = hc
λ
mc = h ⇒λ= h
λ mc
47