d giving

le,

wing
oleculethofe
2
etc., and AtomicStructure
Atom
John Dalton proposed (in l808) that atom is the smallest indivisible
particle of mattep Atomic radii are of the order of 10 cm. It contains
three subatomic particles namely electrons, protons and neutrons.
products
-aning to Electron
Electron was discovered as a result of study of cathode rays by
onsumed JJ Thomson. It was named by Stony
(It carries a unit negative charge (-1.6x 10-9 C))
onsumed Mass of electron is 9.11x 1031 kg and mass of one mole of electron is
0.55 mg) Some of the characteristics of cathode rays are:
an be
G) These travel in straight line away from cathode and produce
fluorescence when strike the glass wallof discharge tube.
ction. (iü) These cause mechanical motion in a small pin wheel placed in
their path.
(iii) These produce X-rays when strike with metal and are deflected
than the byelectric and magneticfield.
ctions. n 7S8 Xl0
Charge toMass Ratio of Electron
In 1897, British physicisteJJ Thomson measured the ratio of electrical
charge (e) to the mass of electron (m,) by using cathode ray tube Jand
other as
applying electrical and magnetic field perpendicular to eachamount of
well as to the path of electrons. Thomson argued that the
deviation of the particles from their path in the presence of electrical or
magnetic field may vary as follows:
greater
e Ifgreater the magnitude of the charge on the particles,
is the deflection.
greater the
. The mass of the particle, lighter the particle,
deflection.
16 Handbook of Chemistry
electrons from its original path increase with
(üi The deflection of voltage. By this Thomson determined the
theincrease in the kgl
value e m,as 1.758820 x 1o'" C

(Proton mas= |-67% lo k ray experiment.

on the basis of anode
Rutherford discovered proton
10" C).
It carries a unit positive charge (+1.6 x
u.
The mass of proton is 1.007276
maximum for
ratio of proton is 9.58× 10 C lg. (m ratio is
e
The
m

hydrogen gas.)
Some of the characteristics of anode rays are:
i) These travel in straight line and possess mass many times
heavier than the mass of an electron.
(iü) These are not originated from anode but are produced in the
space between the anode and the cathode.
(ii) These also cause mechanical motion and are deflected by electric
and magnetic field.
(iv) Specific chargefor these rays depends upon the nature of
the gas taken and is maximum for H.
Neutron
Neutrons are neutral particles. It was discovered by Chadwick (1932).
The mass of neutron is 1.675x 10 * g or 1.008665 amu or u.
Be + He
(a'-particles) (Neutron)
Some ther Subatomic Particles
(a) Positron Positive electron (e),
and Anderson (1932).
discovered by Dirac (1930)
(b) Neutrino and antineutrino Particles of small mass and
charge as stated by Fermi (1934). no
(c) Meson Discovered by
Yukawa (1935) and Kemmer. They are
unstable particles and include pi ions r, or t].
(d) Anti-proton It is
Weigland (1955). negative proton produced by Segre and
 Atomic Structure 17

Thomson's Atomic Model

Atom is a positivesphere with a number of electrons distributedwithin
the sphere. It is also known as plum pudding model. It explains the
neutrality of an atom. This model could not explain the results of
Rutherford scattering experiment.

Rútherford's Nuclear Model of Atom

It is based upon a-particle scattering experiment. Rutherford
presented that
() most part of the atom is empty.
(11) atom possesses a highly dense, positively charged centre, called
nucleus of the order 10 cm.
(iii) entire mass of the atom is concentrated inside the nucleus.
(iv) electrons revolve around the nucleus in circularorbits.
(v) electrons and the nucleus are held together by electrostatic
forces of attraction.

Drawbacks of Rutherford's Model

(i) According toelectromagnetic theory, when charged particles are
accelerated, they emit electromagnetic radiations, which comes
by electronic motion and thus orbit continue to shrink, so atom is
unstable. It doesn't explain the stability of atom.
(ii) It doesn't say anything about the electronic distribution around
nucleus.

Atomic Number (Z) = no h p

Atomic number of an element corresponds to the total number of
protons present in the nucleus or total number of electrons present in
the neutral atom.

Mass Number (A)

The mass of the nucleus is due to protons and neutrons, thus they are
collectively called nucleons.)The total number of nucleons is termed
as mass number of the atom.
|Mass number of an element = number of protons + number of neutrons
Representation of an Atom
Mass number
Symbol of the element
Atomic number
18 Handbook of Chemistry
Different Types of Atomic Species
La Tsotopes Species with same atomicnumber but different mass
number are called isotopes, e.g. H, H.
Loy Isobars Species with same mass number but different atomic
number are called isobars, e.g. 1gAr,1gk40
(c) Isotones Species having same number of neutronsare called
isotones, e.g. H° and ,He* are isotenes.
(d) Isodiaphers Species with samne isetpic number are called
isodiaphers, e.g. 1gK,
Isotopic number = mass number - [2 x atomic number]
Ler isoelectronic Species with same number of electrons are
called isoelectronic speices, e.g. Na, Mg.
() Isosters Species having same number of atoms and same
number of electrons, are called isosters, e.g. N, and CO.

Developments Leading to the Bohr's Modelof Atom

Two developments played a major role in theformulation of Bohr's model:
(i) Dual character of the electromagnetic radiation which
means
that radiation possess wave like and particle like properties.
(ii) Atomic spectra explained by electronic energy level in atoms.

Electromagnetic Wave Theory (Maxwell)

The energy is emitted from source continuously in the form
radiations and magnetic fields. All electromagnetic waves travel with of
the velocity of light (3 x 10° m/s) and do not require any
medium for
their propagation.
An electromagnetic wave has the following
characteristics:
.Wavelength It is the distance between two
successive crests
or troughsof a wave. It is denoted by the Greek letter à (lambda).
) Frequency lt represents the
number of waves which pass
through a given point in one second. It is denoted by v(nu).
) Velocity (v) It is defined as the distance
by the waves. Velocity of light is 3x 10 cms
covered in one secónd
(i Wave number It is the reciprocal of wavelength and has units
em. It is denoted by v (nu bar).
() Amplitude (a) It is the height of the crest or depth of the
trough of a wave.
 Atomic Structure 19

Wavelength (), frequency (v) and velocity (v) of any electromagnetic

v = và.
radiations are related to each other as
Electromagnetic wave theory was successful in explaining the
properties of light such as interference, diffraction etc., but it could not
explain the
1. Black body radiation
2. Photoelectric effect
These phenomena could be explained only if electromagnetic waves are
supposed to have particle nature. Max Planck provided an explanation
for the behaviour of black body and photoelectriceffect.

Particle Nature of Electromagnetic Radiation :

Planck's Quantum Theory
from black
Planck explain the distribution of intensity of the radiation different
wavelength at
body as a function of frequency or
temperatures.
hc (: c= v)
E= hy=

1034 J-s
where, h= Planck's constant = 6.63 x
E=energy of photon or quantum
radiation
V= frequency of emitted
frequency and E be total
Ifn is the number of quanta of a particular
energy then
E =nhv

BlackBody Radiation emitted is

substance being heated is a black body, the radiation
If the
called black body radiation.
Photoelectric Effect
phenomenon in which beam of light of certain frequency falls
It is the electrons are ejected from it.
on the surface of metal and
known as photoelectric effect. It was first observed
This phenomenon is
by Hertz. hv
Wo = hvo 1 my2
hc
Wo= Metal hNo [work function]
max
20 Handbook of Chemistry
minimum frequency of the radiation
Threshold frequency (V,) = minimum energy of the radation
required
Work function (Wo)=
E= KE+ Wo
1 [Kinetic energy of ejected electron = h(v - Vol
mu = h(v- V)
2
incident radiation
where, V= frequency of
VÍ = threshold frequency
Electromagnetic Spectrum
of electromagnetic radiations differ only in their
The different types these electromagnetic
wavelengths and hence, frequencies. (When
increasing wavelengths or
radiations are arranged in order of their obtained is called
spectrum
decreasing frequencies, the complete
electromagnetic spectrum.
Different Types of Radiations and Their Sources
Generation source
Type of radiation Wavelength (in A)
Gamma rays 0.01 to 0.1 Radioactive disintegration
0.1 to 150 From mnetal when an electron strikes on it
X-rays
UV-rays 150 to 3800 Sun rays
Visible rays 3800 to 7600 Stars, arc lamps
Infrared rays 7600 to 6 x 10° Incandescent objects
Micro waves 6x 10 to 3x10Klystron tube
Radio waves 3x 104 From an alternating current of high
frequency
Electromagnetic spectra may be emission or absorption spectrum on
the basis of energy absorbed or emitted An emission spectrum is
obtained when a substance emits radiation after absorbing energy An
absorption spectra is obtained when a substance absorbs certain
wavelengths and leave dark spaces n bright continuous spectrum.
A spectrum can be further classified into two categories such as
)Continuous or band spectrum A spectrum in which there is
nosharp boundary between two different radiations.
(ii) iscontinuous or line spectrum A spectrum in which
radiations of a particular wavelength are separated from each
other through sharp boundaries.
 Atomic Structure 21

Bohr's Model
Neils Bohr proposed his model in 1931. Bohr's model is applicable only
for one electron system like H, He,Lit etc.
Assumptions of Bohr's model are
Electrons keep revolving around the nucleus in certain fixed
permissible orbits where it doesn't gain or lose energy. These
orbits are known as stationary orbits.
circumference of orbit
Number of waves in an orbit =
wavelength
2. Theelectrons can move only in those orbits for which the angular
momentum is an integral multiple of i.e.
2c
nh
mur = (n =1,2, 3.....)
2Tt
where, m = mass of electron;U= velocity of electron;
r= radius of orbit
n= number of orbit in which electrons are present
8. Energy is emitted or absorbed only when an electron jumps from
higher energy level to lower energy level and vice-versa.
hc
AE =E, - E, = hv=
A. The most stable state of an atom is its ground state or normal
state.
From Bohr's model, energy, velocity and radius of an electron in
nth Bohr orbit are
(i) Velocity of an electron in nth Bohr orbit
(u,)= 2.165 × 106 n
m/s

(ii) Radius of nth Bohr orbit

n
l0-10 m = 0.53
(C,)= 0.53 × Z
22
(iii) B, =- 2.178 x 10-l8 n2 Jlatom
22
=- 1312 kJ/ mol

13.6,
n2 eVlatom
 22 Handbook of Chemistry
1
AE=- 2.178x 10-l8 z Jlatom
where, n =number of shell; Z= atomic number
As we go away from the nucleus, the energy levels come closer
i.e. with the increase in the value of n, the difference of
between successive orbits decreases.
energy
E,- E, >E, - E, >E, - E, >E, - E, etc.
Thus,
Emission Spectrum of Hydrogen
According to Bohr's theory, when an electron jumps from ground state to
excited state, it emits a radiation of definite frequency (or wavelength),
Corresponding to the wavelength of each photon of light emitted,a
bright line appears in the spectrum.
The number of spectral lines in the spectrum when the electron comes
from nth level to the ground level = n(n -1)

Hydrogen spectrum consist of line spectrum.

Series Region
Lyman UV 1 2. 3, 4, ...
GBalmer Visible 2 3, 4, 5, ...
Paschen IR 3 4, 5, 6, ...
L Brackett IR 5, 6, 7, ...
W
Pfund far IR 5 6, 7, .
A)Humphery far IR 6 7, 8, 9,
Wave number (v) is defined as reciprocal of the wavelength.
’V=RZ?|1 1
2
n
where, n =1,2......
ng = n +1, n, + 2....
Here, = wavelength
R= Rydberg constant = 109677.8cm
First line of a series is called line of longest wavelength (shortest
energy) and last line of a series is the line of shortest wavelength
(highest energy, ng =o).)
 Atomic Structure 23

YSommerfeld Extension to Bohr's Model

According to this theory, the angular momentum of revolving electron
h
in an elliptical orbit is an integral multiple of i.e.
2T
kh
mur =
2T
nh
From Bohr model, mur

For K shell, n =1, k= 1Circular shape

Lshell, n = 2, k=1,2Circular
M shell, n =3, k= 1,2, 3Elliptical
N shell, n=4, k= 1, 2,3, 4Eliptical
imitationsof Bohr's Theory
) It is unable toexplain the spectrum of atom other than hydrogen
like doublets or multielectronatoms.
(i) It could not explain the ability of atom to form molecules by
chemical bonds. Hence, it could not predict the shape of
molecules.
(ii) Itis not in accordance with the Heisenberg uncertainty principle
and could not explain the concept of dual character of matter.
(iv) It is unable to explain the splitting of spectral lines in the
presence of magnetic field (Zeeman effect) and electric field
(Stark effect).
Towards Quantum Mechanical Model ofthe Atom
Two important developments which contributed significantly in the
formulation of such a model were given below
(1. de-Broglie Principle (Dual Nature)
de-Broglie explains the dual nature of electron, i.e. both particle as well
as wave nature.
h
A= Or =2 [p=mv (momentum)]
mU

Where, A= wavelength; v= velocity of particle; m = mass of particle

2=
V2m x KE
where, KE =kinetic energy.
 Atomic Structure 25

Difference between Orbit and Orbital

Orbit Orbital
1. An orbit is a well defined circular path An orbital is the three dimensional space
around the nucleus in which the around the nucleus within which the
electron revolves. probability of finding an electron is maximum.
2. The maximum number of electrons in The maximum number of electrons present
any orbit is given by2n
2rf where n is the in any orbital is two.
number of the orbit.

Shapes of Atomic Orbitals

Theshapes of the orbitals are
s-spherical, p-dumb bell, d-double-dumb-bell, f-Diffused
These orbitals combine to form subshell.
) ssubshell will have only one spherical orbital.
Y
(Sp'eal
>X
ddoube donbb e
three orbitals (p. , D.. D.).Icomp
(1) psubshell has Py
 Atomic Structure 27
Node
A region or space, where probability of finding an electron is
maximum, is called a peak, while zero probability space is called node.
Nodes are of two types :
(a) Radial nodes (b) Angular nodes
(i) (n -l- 1)=radial node
(ii) ()= angular node
(iii) (n -1)= total nodes

Number of Peaks and Nodes for Various Orbitals

S. No. Type of orbital Number of peaks Number of nodes

1 n-1

2. n -1 n-2

3. d n-2 n-3

4. f n-3 n- 4

Quantum Numbers
Each electron in an atom is identified in terms of four quantum numbers.
Principal Quantum Number (Neils Bohr)
It is denoted by n. It tells us about the main shell in which electron
resides, It also gives an idea about the energy of shell and average
distance of the electron from the nucleus. Value of n = any integer.
Azimuthal Quantum Number (Sommerfeld)
It is denoted by l. It tells about the number of subshells (s, p, d, f) in
any main shell. It also represents the angular momentum of an
electron and shapes of subshells. The orbital angular momentum of an
h
electron =J(l+1) 2Tt
Value of l= 0to n- 1.
l=0for s, l= 2 for d
l=1for p, l= 3for f
Number of subshells in main energy level = n.
Magnetic Quantum Number (Lande)
1 1s denoted by m. It tells about the number of orbitals and orientation
of each subshell. Value of m=-l to+l including zero.
Number of orbitals in each subshell = (2l + 1)
 28 Handbook ofChemistry
Subshell Orbital Pauli Exclusion Pri
S. No.
1 It states, no two ele
1. S
3
quantum numbers,
2. p The maximumn numt
d 5
3. dsubshell is 10 and
f 7
4.
Hund's Rule of Ma
level =n.
Number of orbitals in main energy It states,
shell =2n
Maximum number of electrons in nth (i) In an atom no e
until each orbi
Goldsmith)
Spin Quantum Number (Ublenbeck and (ii) The unpaired
spinning of
It is denoted by m, or s. It indicates the direction of same subshell
electron, i.e. clockwise or anti-clockwise. Methods of Writi
Maximum number of electrons in main energy level = 2n
(i)) Orbital metI
orbitals are de
Electronic Configuration
Arrangement of electrons in various shells, subshells and orbitals in an (ii) Shell metho
atom is known as electronic configuration. continuously

Fillingof Orbitals in Atom

Aufbau Principle (iii) Box method
According to this principle, in the ground state of an atom, the and electrons
electrons occupy the lowest energy orbitals available to them, ie. the (T) arrows. An
orbitals are filled in order of increasing value of n +. For the orbitals
having the same value of n +l, the orbtial having lower value of n is e.g.
filled up first.
The general order of increasing energies of the orbital is
ls< 2s < 2p< 3s< 3p< 4s < 3d < 4p< 5s < 4d < 5p<6s< 4f< 5d Half-filled an
more stable. H
<6p< 7s < 5f< 6d < 7p 3a1° 4s'.
Thus, the filling of electrons in various subshells within the atom can
be summerised through following figure. Electronic Configu
1s To write the electro
configuration of neL
2s
3s
2p remove (for positive
4s 3d 3p nature and mnagnitu
5s 4d 4p
6s 4f 5d
5p
6p
7s 5f 6d
7p
The energy of atomic orbitals for
H-atom varies as
ls< 2s = 2p< 3s = 3p= 3d< 4s =
4p=4d = 4f
 Atomic Structure 29

Pauli Exclusion Principle

It states, no two electrons in an atom can have identical set of four
quantum numbers,
The maximum number of electrons in s subshell is 2, psubshell is 6,
d subshell is 10and f subshell is 14.
Hund's Rule of Maximum Multiplicity
It states,
) In an atom noelectron pairing takes place in the p, d or f-orbitals
until each orbital of the given subshell contains one electron.
(ii) The unpaired electrons present in the various orbitals of the
same subshell should have parallel spins.
Methods of Writing Electronic Configuration
) Orbital method In this, the electrons present in respective
orbitals are denoted. e.g. Cl(17) =1s,2s,2p, 3s, 3p.
(iü) Shell method In this, the number of electrons in each shell is
continuously written. e.g. Cl (17) = ls,2s*, 2p,3s,3p
K L M
2, 8, 7
(iii) Box method In this method, each orbital is denoted by a box
and electrons are represented by half-headed (1) or full-headed
(T) arrows. An orbital can occupy a maximum of two electrons.
e.g.

12 2s2 2p6 3s2 3p5

Half-filled and completely filled electronic configurations are
more stable. Hence, outer configuration of Cr is 3d° 4s and Cu is
3d1°4s'.
Electronic Configuration of lons
To write the electronic configuration of ions, first write the electronic
configuration of neutral atom and then add (for negative charge) or
remove (for positive charge) electrons in outer shell according to the
nature and magnitude of charge present on the ion. e.g.
O(8) = ls,2s²2p, 0 (10) = ls', 2s2p®