2.

Structure of Atom
FUNDAMENTAL PARTICLES: Electron, Proton and Neutron

Atomic Number(Z) and Mass Number (A)

Atomic number (Z) = The number of protons in an atom / ion (or)
no. of electrons in an atom is equal to atomic number (Z ).
Protons and neutrons present in the nucleus are known as nucleons.
Mass number (A) = number of protons (Z) + number of neutrons (n)
Isotopes are atoms with same atomic number but different mass numbers.
12 13 14 1 2 3
Eg: (i) 6 C, 6 C, 6 C (ii) 1 H, 1 D , 1 T

Isobars are the atoms with same mass number but different atomic number.
14 14
Eg: 6 C and 7 N.

Electromagnetic Radiation: it is a form of radiant energy which propagates through space in the
form of a wave, associated with both electric field and magnetic field.
There are many types of electromagnetic radiations, which differ from one another in wavelength
(or frequency). These constitute what is called electromagnetic spectrum.

Characteristics of electromagnetic radiation:

frequency () and wavelength (λ), wave number ( ), velocity (c) and amplitude.
Frequency (ν ) is defined as the number of waves that pass a given point in one second (Hz, s-1).
Wavenumber( ): is defined as the number of wavelengths per unit length. Its units are reciprocal of
wavelength unit, i.e., m-1.
The frequency (ν ), wavelength (λ) and velocity of light (c) are related by the equation .
c=νλ
Wave Number ( ): It is the number of waves spread in 1 cm. length.
Planck’s Quantum Theory:
(i) Energy is emitted (or absorbed) not continuously but discontinuously in the form of small packets
called quanta.
(ii) The energy (E) of a quantum of radiation is proportional to its frequency (ν ) and is expressed by
equation. E = hν , „h‟ is known as Planck‟s constant = 6.626×10-34 J s.
(iii) The energy of electron is quantized and is equal to integral multiple of hv (n=1,2,3,…) .
E = n hν 9 N=1,2,3 ……….)

The ideal body, which emits and absorbs all frequencies, is called a black body and the radiation
emitted by such a body is called black body radiation.
At a given temperature, intensity of radiation emitted increases with decrease of wavelength,
reaches a maximum value at a given wavelength and then starts decreasing with further decrease of
wavelength, as shown.

Photoelectric Effect: A phenomenon of ejection of electrons from the surface of metal when a light
of certain frequency falls on it.
Eg: potassium, rubidium, caesium etc.

(i) The number of electrons ejected is proportional to the intensity or brightness of light.
(ii) For each metal, there is a characteristic minimum frequency, ν 0 (also known as threshold
frequency) below which photoelectric effect is not observed.
At a frequency ν >ν0, the ejected electrons come out with certain kinetic energy. The kinetic
energies of these electrons increase with the increase of frequency of the light used.
Kinetic energy of the ejected electron is proportional to the frequency of the electromagnetic
radiation. Since the striking photon has energy equal to hν and the minimum energy required to
eject the electron is hν0 (also called work function, W0 ), then the difference in energy (hν – hν0 ) is
transferred as the kinetic energy of the photoelectron.
hv = hv0 + ½ m v2
where m is the mass of the electron and v is the velocity associated with the ejected electron.

BOHR’S MODEL FOR HYDROGEN ATOM

Postulates:
i) The electrons revolve around the nucleus in a circular path called orbits.
n=1, 2, 3…… or K, L, M …
(ii)These are orbits are associated with definite amount of energy called energy shells.
(iii) The energy of an electron in the orbit does not change with time. Hence these energy shells are
stationary states.
(iv) The electron will move from a lower stationary state to a higher stationary state when required
amount of energy is absorbed by the electron or energy is emitted when electron moves from higher
stationary state to lower stationary state.
(v) The frequency of radiation absorbed or emitted when transition occurs between two stationary
states that differ in energy by ΔE, is given by :
ν = ΔE/h = (E2 – E1)/h
Where E1 and E2 are the energies of the lower and higher allowed energy states respectively.
iv) The angular momentum of an electron is quantized and is equal to integral multiple of n h/2π
m Vr = nh/2π
Limitations of Bohr’s Model
i) Bohr‟s theory was unable to explain the splitting of spectral lines in the presence of magnetic field
(Zeeman Effect) or an electric field (Stark effect).
ii) It could not explain the ability of atoms to form molecules by chemical bonds.

Zeeman effect: It is splitting of spectral lines in magnetic field

Stark Effect: It is splitting of spectral lines in electric field

Quantization of Electronic Energy Levels

Quantization: it is the restriction of any property to discrete values is called quantization.
Emission Spectra and Absorption Spectra
The spectrum of radiation emitted by a substance that has absorbed energy is called an emission
spectrum.
The spectrum of radiation obtained when a radiation is passed through a substance which absorbs
radiation of certain wavelength is called an absorption spectrum.
Emission spectrum leaves bright spaces in the dark continuous spectrum whereas absorption
spectrum leaves dark spaces in the bright continuous spectrum.
The study of emission or absorption spectra is referred to as spectroscopy.

Line Spectrum of Hydrogen

Rydberg suggested that all series of lines in the hydrogen spectrum could be described by the
following expression :

where n1 = 1,2…….. n2 = n1 + 1, n1 + 2………..

The value 109,677 cm-1 is called the Rydberg constant for hydrogen. The first five series of lines that
correspond to n1 = 1, 2, 3, 4, 5 are known as Lyman, Balmer, Paschen, Bracket and Pfund series,
respectively.

SE RI E S N1 N2 SP E C TRAL RE G I ON

Lyman 1 2,3…. Ultraviolet

Balmer 2 3,4…. Visible

Paschen 3 4,5…. Infrared

Brackett 4 5,6…. Infrared

Pfund 5 6,7…. Infrared

However, according to Bohr‟s theory for hydrogen atom:

i) The radii of the stationary states are expressed as : rn = n2 X 52.9 pm
for hydrogen – like ion (1 electron system) rn = 52.9(n2)/Z pm
ii)the energy of its stationary state En = − 2.18×10-18 J atom-1(1/n2) n=1,2,3…..
= − 1.316×10-6 J mol-1(1/n2)
for hydrogen – like ion (1 electron system), En = − 2.18×10-18X Z2 (1/n2) n=1,2,3…..

What does the negative electronic energy (En) for hydrogen atom mean?

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 is an electron that is infinitely far away from the
nucleus and is assigned the energy value of zero. When the electron is free from the influence of
nucleus, the energy is taken as zero. The electron in this situation is associated with the stationary
state of Principal Quantum number (n = ∞) and is called as ionized hydrogen atom. When the
electron is attracted by the nucleus and is present in orbit n, the energy is emitted and its energy is
lowered. That is the reason for the presence of negative sign and depicts its stability relative to the
reference state of zero energy and n = ∞.

Dual Behaviour of Matter

Matter waves: The waves associated with the particle in motion.
Electromagnetic waves Matter waves
1 Has velocity equal to velocity of light Has velocity less than velocity of light
2 It is associated with both electric field No electric field and magnetic field
and magnetic field
3 Have wavelength ( = C/ ν) Have wavelength ( = h/ mv)

de Broglie equation: An equation that shows the relation between wavelength (λ) and momentum
(p) of a material particle.
“Electron behaves as matter waves of wave length λ = h/mv and in its atomic orbitals, it exists as
stationary wave”
λ = h/mv =h/p
where m is the mass of the particle, v its velocity and p its momentum.
It is applicable to the objects of smaller masses.
For objects of larger masses, the wavelengths associated with ordinary objects are so short (because
of their large masses) and therefore, their wave properties cannot be detected.

Heisenberg’s Uncertainty Principle

It states that “it is impossible to determine simultaneously, the exact position and exact momentum
(or velocity) of an electron.”
Mathematically, ΔX x Δpx ≥ h/4π or ΔX x Δ(mvx) ≥ h/4π or ΔX x Δvx ≥ h/4πm
where Δx is the uncertainty in position and Δpx ( or Δv x) is the uncertainty in momentum (or
velocity) of the particle. If the position of the electron is known with high degree of accuracy (Δx is
small), then the velocity of the electron will be uncertain [Δ(v x) is large]. On the other hand, if the
velocity of the electron is known precisely (Δ(v x ) is small), then the position of the electron will be
uncertain (Δx will be large).
Significance of Uncertainty Principle: it rules out existence of definite paths or trajectories of
electrons and other similar particles.
QUANTUM MECHANICAL MODEL OF ATOM
The branch of science that takes into account this dual behaviour of matter is called quantum
mechanics.
Quantum mechanics was developed independently by Werner Heisenberg and Erwin Schrödinger.

Schrödinger wave equation:

Where is a mathematical operator called Hamiltonian. E is the total energy of the system takes
into account the kinetic energies of all the sub-atomic particles and ψ is wave function (amplitude
wave function) Solution of this equation gives E and ψ.
Schrödinger equation gives the possible energy levels the electron can occupy and the corresponding
wave function(s) (ψ) of the electron associated with each energy level.
The quantized energy states and corresponding wave functions which are characterized by a set of
three quantum numbers (principal quantum number n, azimuthal quantum number l and magnetic
quantum number ml ).
The wave function (ψ) is a mathematical function whose value depends upon the coordinates of the
electron in the atom and does not carry any physical meaning.
The wave functions of an electron in an atom are called atomic orbital.
Ψ gives the amplitude of a wave whereas |ψ|2 gives the probability of finding an electron at a point
within an atom.

Important Features of the Quantum Mechanical Model of Atom

1. The energy of electrons in atoms is quantized.

2. The existence of quantized electronic energy levels is a direct result of the wave like properties
of electrons.
3. Both the exact position and exact velocity of an electron in an atom cannot be determined.
4. An atomic orbital is the wave function ψ for an electron in an atom.
5. The probability of finding an electron at a point within an atom is proportional to the square of
the orbital wave function i.e., |ψ|2 at that point. |ψ|2 is known as probability density and is always
positive.
Quantum Numbers
Qualitatively atomic orbitals can be distinguished by their size, shape and orientation. These atomic
orbitals are precisely distinguished by quantum numbers.
Principal quantum number ‘n’
Value of n = 1,2,3……. Or K,L,M….
It determines the size and the energy of the orbital.
It also identifies the shell. n = 1 2 3 4 ………… Shell = K L M N …………
It determines the maximum number of electrons in each shell (upto n = 4) is 2n 2.

Azimuthal quantum number (l) is also known as orbital angular momentum or subsidiary quantum
number. l can have values ranging from 0 to (n – 1), and total values are equal to n. that is, for a
given value of n, the possible value of l are : l = 0, 1, 2, ………. (n-1)
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.
It defines the three dimensional shape of the orbital.
Each shell consists of one or more subshells or sub-levels. The number of subshells in a principal
shell is equal to the value of n. 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

Magnetic orbital quantum number. „ml‟ gives information about the spatial orientation of the
orbital with respect to standard set of co-ordinate axis. For any sub-shell (defined by „l‟ value) 2l+1
values of ml are possible and these values are given by : ml = -l, – (l-1), – (l-2)… 0,1… (l-2), (l-1), l
Thus for l = 0, the only permitted value of ml = 0, [2(0)+1 = 1, one s orbital]. For l = 1, ml can be -1,
0 and +1 [2(1)+1 = 3, three p orbitals]. For l = 2, m l = -2, -1, 0, +1 and +2, [2(2)+1 = 5, five d
orbitals]. It should be noted that the values of ml are derived from l and that the value of l are
derived from n.
Electron spin ‘s’ : The orientations of electrons are distinguished by the spin quantum numbers m s
which can take the values of + or - and are normally represented by two arrows, ↑ (spin up) and ↓
(spin down). Two electrons that have different m s values (one +1/2 and the other -1/2) are said to
have opposite spins.
 Orbit Orbital
1 It is a circular path where It is the wave function of an electron in an
electron revolves around the atom
nucleus.
2 It represents planar motion for It represents 3 dimensional for an electron
electron
3 It gives a definite path for an No definite path but can move within the
electron region
4 These are circular This can be any shape
5 It can accommodate more than It can accommodate not more than
2 electron 2 electron

Shapes of Atomic Orbitals – it is the surface of constant probability density that enclosed some large
fraction (90%) of the probability of finding the electron.

p-orbital: l = 1) m= -1, 0, +1. They are given the designations 2px, 2py, and 2pz.

d-orbital : For l = 2, the orbital is known as d-orbital. There are five ml values (-2, -1, 0, +1 and +2)
for l = 2 and thus there are five d orbitals.
The five d-orbitals are designated as dxy, dyz, dxz, dx2-y2 and dz2.
ELECTRONIC CONFIGURATION OF ELEMENTS
Filling of Orbitals in Atom
The filling of electrons into the orbitals of different atoms takes place according to the aufbau
principle which is based on the Pauli‟s exclusion principle, the Hund‟s rule of maximum multiplicity
and the relative energies of the orbitals.
Aufbau Principle
“In the ground state of the atoms, the orbitals are filled in order of their increasing energies.”
(OR)
“Orbital of lower energy is filled first then the orbitals of higher energy”

In other words, electrons first occupy the lowest energy orbital available to them and enter into
higher energy orbitals only after the lower energy orbitals are filled.
The order in which the energies of the orbitals increase and hence the order in which the orbitals
are filled is as follows :
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, 6p, 7s…

Pauli Exclusion Principle

“No two electrons in an atom can have the same set of four quantum numbers. ”
Pauli exclusion principle can also be stated as : “Only two electrons may exist in the same orbital
and these electrons must have opposite spin.”
This can be summed up as : the maximum number of electrons in the shell with principal quantum
number n is equal to 2n2.
Hund’s Rule of Maximum Multiplicity
Orbitals of equal energy, called degenerate orbitals.
“ pairing of electrons in the orbitals belonging to the same subshell (p, d or f) does not take place
until each orbital belonging to that subshell has got one electron each i.e., it is singly occupied.”
Since there are three p, five d and seven f orbitals, therefore, the pairing of electrons will start in
the p, d and f orbitals with the entry of 4th, 6th and 8th electron, respectively. It has been observed
that half filled and fully filled degenerate set of orbitals acquire extra stability due to their
symmetry
Electronic Configuration of Atoms
H = 1s1
He = 1s2
Li = 1s22s1.
Be = 1s2 2s2
B = 1s22s22p2
C = 1s22s22p2
N = 1s22s22p3
O = 1s22s22p4
F = 1s22s22p5
Ne = 1s22s22p6
The orbital picture of these elements can be represented as follows:

Deviation in electronic configuration of Cr & Cu:

Cr = 1s22s22p63s23p64s23d4 Cu = 1s22s22p63s23p64s23d9
Modified as:
Cr = 1s22s22p63s23p64s13d5 Cu = 1s22s22p63s23p64s13d10
Reason: (i) symmetry leads to stability : Stability of Completely Filled and Half Filled Subshells
(ii) due to exchange energy( the enthalpy change when electron of same spin exchanges its
position within same sub-shell