STRUCTURE OF ATOM

 Atom – term given by Dalton expected from negatively charged from their path and hit the
 Greek word a-tomio which particles cathode ray tube at point A
means non-divisible  cathode rays consist of negatively  when only magnetic field is
 Dalton’s atomic theory was able charged particles, called electrons applied, electron strikes the
to explain the law of conservation  cathode rays (electrons) do not cathode ray tube at point C
of mass, law of constant depend upon the material of
composition and law of multiple electrodes and the nature of the
proportion gas present in the cathode ray
 He failed to explain internal tube.
structure of atom  J.J. Thomson measured the ratio
 Electrical discharge in partially of electrical charge (e) to the
e 11 −1
evacuated tubes, known as mass of electron (m ) by using  =1.75 × 10 C kg
m
cathode ray discharge tubes cathode ray tube
 Mulliken oil drop experiment to
 The electrical discharge through  Electrons discovered by J. J determine the charge on the
the gases could be observed only Thomson but named by Stoney electrons
at very low pressures and at very  applying electrical and magnetic  Anode rays or canal rays
high voltages field perpendicular to each other discovered by gold stein
 Cathode rays as well as to the path of electrons
 Depends upon the nature of gas
the amount of deviation of the
 The flow of current from cathode present in the cathode ray tube.
particles from their path in the
to anode was further checked by  The charge to mass ratio of the
presence of electrical or magnetic
making a hole in the anode and particles is found to depend on
field depends upon
coating the tube behind anode the gas from which these
with phosphorescent material  The magnitude of the negative
originate.
zinc sulphide. charge (directly proportional) on
the particle  The smallest and lightest positive
 The cathode rays start from ion was obtained from hydrogen
cathode and move towards the  The mass of the particle —
and was called proton
anode. lighter the particle, greater the
 Neutron
deflection
 These rays are not visible but
 The strength of the electrical or  discovered by Chadwick by
their behaviour can be observed
magnetic field bombarding a thin sheet of
with the help of certain kind of
beryllium by α-particles
materials (fluorescent or  deflection of electrons from its
9 4 12 1
phosphorescent) original path increases with the  4 Be + 2 He → 6C + 0 N
 In the absence of electrical or increase in the voltage across the  Its mass slightly greater than that
magnetic field, these rays travel electrodes, or the strength of the of the protons
in straight lines magnetic field  J. J. Thomson proposed that an
 In the presence of electrical or  When only Electric field is atom possesses a spherical shape
magnetic field, the behaviour of applied, the electrons deviate (radius approximately 10–10 m) in
cathode rays are similar to that
 STRUCTURE OF ATOM

which the positive charge is charge and four unit of atomic volume that repelled and
uniformly distributed. mass. deflected the positively charged
 The electrons are embedded into  β-rays are negatively charged α– particles
it in such a manner as to give the particles similar to electrons.  The radius of the atom is about
most stable electrostatic  The γ-rays are high energy 10 –10 m, while that of nucleus is
arrangement radiations like X-rays and are 10 –15 m
 Also called as plum pudding, neutral in nature and do not  Rutherford proposed the nuclear
raisin pudding or watermelon consist of particles model of atom after the discovery
 mass of the atom is assumed to be  penetrating power - α-particles of protons
uniformly distributed are the least, followed by β-rays  The positive charge and most of
 model was able to explain the (100 times that of α–particles) the mass of the atom was densely
overall neutrality of the atom and γ-rays (1000 times of that α- concentrated in extremely small
 Thomson was awarded Nobel particles). region called as nucleus
Prize for his theoretical and  Rutherford and his students (Hans  The nucleus is surrounded by
experimental investigations on Geiger and Ernest Marsden) electrons that move around the
the conduction of electricity by bombarded very thin gold foil nucleus with a very high speed in
gases circular paths called orbits
with α–particles
 Röentgen discovered X rays  Electrons and the nucleus are
 α–particles from a radioactive
 X-rays are produced effectively held together by electrostatic
source was directed at a thin foil
when electrons strike the dense forces of attraction.
(thickness ∼ 100 nm) of gold
metal anode, called targets  Mass of moving electron
metal
 These are not deflected by the Mo
 observations M=

√ ()
electric and magnetic fields and 2
 most of the α– particles passed v
1−
have a very high penetrating c
through the gold foil undeflected
power through the matter  Atomic number (Z) = number of
 a small fraction of the α–particles
 These rays are of very short protons in the nucleus of an atom
was deflected by small angles
wavelengths (∼0.1 nm) and = number of electrons in a neutral
 a very few α– particles (∼1 in atom
possess electro-magnetic
20,000) bounced back, that is,  protons and neutrons present in
character
were deflected by nearly 180 the nucleus are collectively
 Becqueral observed that there are
 conclusion known as nucleons
certain elements which emit
radiation on their own -  Most of the space in the atom is  mass number (A) = number of
radioactivity and the elements empty as most of the α–particles protons (Z) + number of neutrons
known as radioactive elements passed through the foil  Element can be represented by
 Rutherford found that α-rays undeflected A
X
Z
consists of high energy particles  The positive charge has to be
carrying two units of positive concentrated in a very small
 STRUCTURE OF ATOM

 Isobars are the atoms with same  According to the electromagnetic  The oscillating electric and
mass number but different atomic theory of Maxwell, charged magnetic fields produced by
number particles when accelerated should oscillating charged particles are
 atoms with identical atomic emit electromagnetic radiation perpendicular to each other and
number but different atomic mass  It should take an electron only both are perpendicular to the
number are known as Isotopes 10 –8 s to spiral into the nucleus direction of propagation of the
 The isotopes is due to the But this does not happen wave
presence of different number of  Rutherford model cannot explain  Unlike sound waves or water
neutrons present in the nucleus the stability of an atom waves, electromagnetic waves do
 99.985% of hydrogen atoms  Approx size of nucleus not require medium and can
contain only one proton called 1/ 3
move in vacuum
 r =r o ( A )
protium (11 H ).  radio frequency region around
 A – Atomic mass 106 Hz, used for broadcasting
 The isotope with 1 proton and 1  r o = 1.3 x 10 – 15 m  microwave region around 10 10
neutron is called deuterium (21 D
 1 Fermi = 10 – 15 m Hz used for radar
0.015%)
 α– particles deflection  infrared region around 10 13 Hz
 The isotope with 1 proton and 2
proportional to 1/sin 4 θ used for heating
neutrons is called tritium (31 H )
 Two developments played a  ultraviolet region around 10 16Hz
 Isotones – same number of major role in the formulation of a component of sun’s radiation.
neutrons ( A - Z) Bohr’s model of atom  The small portion around 10 15 Hz
 Isodiaphers – same (A – 2Z)  Dual character of the is what is ordinarily called visible
value electromagnetic radiation which light
 Isosters – same atomicity means that radiations possess c
 chemical properties of atoms are both wave like and particle like  ν=
λ
controlled by the number of properties  c = 3 x 10 8 m/s
electrons, which are determined  atomic spectra which can be  The SI unit for frequency (ν ) is
by the number of protons in the explained only by assuming hertz (Hz, s–1)
nucleus quantized
 The other commonly used
 All the isotopes of a given  James Maxwell suggested that quantity specially in
element show same chemical when electrically charged particle spectroscopy, is the wavenumber
behavior moves under accelaration
 reciprocal of wavelength
 Drawbacks of Rutherford Mode alternating electrical and
1
 when a body is moving in an magnetic fields are produced and  ν=
λ
orbit, it undergoes acceleration transmitted.
 diffraction and interference can
(even if the body is moving with  These fields are transmitted in be explained by the wave nature
a constant speed in an orbit, it the forms of waves called of the electromagnetic radiation
must accelerate because of electromagnetic waves or  Electromagnetic theory failed to
changing direction) electromagnetic radiation explain
 STRUCTURE OF ATOM

 the nature of emission of ejection of electrons from the

radiation from hot bodies (black - metal surface.
body radiation)  The number of electrons ejected
 Ejection of electrons from metal  Planck suggested that atoms and is proportional to the intensity or
surface when radiation strikes it molecules could emit (or absorb) brightness of light
(photoelectric effect) energy only in discrete quantities  Einstein was able to explain the
and not in a continuous manner
 variation of heat capacity of photoelectric effect using
solids as a function of Planck’s quantum theory of
temperature electromagnetic radiation
 line spectra of atoms with special 1 2
 hυ=h υ o + m v
reference to hydrogen 2
 Particle nature of light could
 Explanation for the phenomenon
explain the black body radiation
of the black body radiation was
and photoelectric effect
given by Max Planck
 It is observed that when a ray of
 Diffraction is the bending of
white light is passed through a
wave around an obstacle.  Quantum is the smallest quantity prism the wave with shorter
 Interference is the combination of of energy that can be emitted or wavelength bends more than the
two waves of the same or absorbed in the form of one with a longer wavelength
different frequencies to give a electromagnetic radiation
 The spectrum of white light
wave whose distribution at each  The energy (E ) of a quantum of ranges from violet at 7.5 × 10 14
point in space is the algebraic or radiation is proportional to its Hz to red at 4×10 14 Hz.
vector sum of disturbances at that frequency (ν )  Such a spectrum is called
point resulting from each
hc continuous spectrum
interfering wave.  E = hυ =
λ
 Discontinuous spectrum
 The ideal body, which emits and  h = 6.626×10 – 34 J s
absorbs radiations of all  Emission spectrum
 Photoelectric effect
frequencies, is called a black  Line spectrum in gases
 Hertz performed a experiment in
body and the radiation emitted by  Band spectrum in molecules
which electrons (or electric
such a body is called black body  The spectrum of radiation emitted
current) were ejected when
radiation by a substance that has absorbed
certain metals ( potassium,
 The exact frequency distribution energy is called an emission
rubidium, caesium )
of the emitted radiation (intensity spectrum
 hvo = wo = work fuction
versus frequency curve of the  The study of emission or
radiation) from a black body  The electrons are ejected from the
absorption spectra is referred to
depends only on its temperature metal surface as soon as the beam
as spectroscopy
of light strikes the surface
 At a given temperature, intensity  Such spectra are called line
of radiation emitted increases  There is no time lag between the
spectra or atomic spectra because
with decrease of wavelength striking of light beam and the
the emitted radiation is identified
 STRUCTURE OF ATOM

by the appearance of bright lines  Balmer showed that spectral  The radii of the stationary states
in the spectra lines can be expressed in terms of r on
2

 Line emission spectra are of great wavenumber  rn =

z
interest in the study of electronic  No of lines -  r o =0.529 Å
structure n2−n 1(n2−n1 +1)  Energy
 2
( )
The characteristic lines in atomic z
2

spectra can be used in chemical  Neils Bohr was the first to  En =−R H 2
n
analysis to identify unknown explain quantitatively the general
 where RH is called Rydberg
atoms features of hydrogen atom
constant - 2.18 × 10 - 18 J
 Robert Bunsen was one of the structure and its spectrum.
 Velocity of electron
first investigators to use line  The Energy of an electron in the
spectra to identify elements

orbit does not change with time
The electron in the hydrogen
 V n=2.18 x 106 ( Zn ) m /s
 The energy of the electron in a
atom can move around the
hydrogen atom has a negative
nucleus in a circular path of fixed
sign for all possible orbits
radius and energy. These paths
 A free electron at rest is an
are called orbits
electron that is infinitely far away
 These orbits are arranged
from the nucleus and is assigned
concentrically around the nucleus
the energy value of zero
 Bohr’s frequency rule
 magnitude of velocity of electron
 The frequency of radiation increases with increase of
 Elements like rubidium (Rb), absorbed or emitted when positive charge on the nucleus
caesium (Cs), thallium (Tl), transition occurs between two and decreases with increase of
indium (In), gallium (Ga) and stationary states that differ in principal quantum number
scandium (Sc) were discovered energy by ∆E  ∆ E=E f – Ei
when their minerals were
analysed by spectroscopic
methods
 υ=
ΔΕ Ε 2−Ε1
h
=
h  ∆ E=R H Z
2
( 1 1
2
− 2
n1 n2 )
 The angular momentum of an 
 The element helium (He) was electron in a given stationary
discovered in the sun by
spectroscopic method.
state
nh
ν=1.09677 x 10
7
( 1 1 −1
2
− 2 m
n 1 n2 )
 me vr=  The brightness or intensity of
2π
spectral lines depends upon the
 angular momentum is integral
number of photons of same
multiple of h/2π
wavelength or frequency
 The stationary states for electron absorbed or emitted
are numbered n = 1,2,3 are
 Limitations of Bohr’s Model
known as Principal quantum
numbers
 STRUCTURE OF ATOM

 The wave character of the by Werner Heisenberg and Erwin  Both the exact position and exact
electron is not considered in Bohr Schrödinger velocity of an electron in an atom
model  The fundamental equation of cannot be determined
 It could account for the stability quantum mechanics was simultaneously
and line spectra of hydrogen atom developed by Schrödinger and  An atomic orbital is the wave
and hydrogen like ions won the Nobel Prize function ψ for an electron in an
 Unable to explain the splitting of  H ψ = Eψ where H is a atom
spectral lines in the presence of mathematical operator called  2
(ψ ) is known as probability
magnetic field (Zeeman effect) or Hamiltonian density and is always positive
an electric field (Stark effect)  These quantized energy states and  The principal quantum number
 It could not explain the ability of corresponding wave functions  The principal quantum number
atoms to form molecules by which are characterized by a set determines the size and to large
chemical bonds of Three quantum numbers extent the Energy of the orbital
h h h (principal quantum number n,
 λ= = =  The increase in the value of n ,
mv P √ 2 mK . E azimuthal quantum number l and
the number of allowed orbital
 An electron microscope is a magnetic quantum number ml )
increases and are given by n 2
powerful tool in modern scientific arise as a natural consequence in
the solution of the Schrödinger  The Energy of the orbital will
research because it achieves a
equation increase with increase of n
magnification of about 15 million
 Azimuthal quantum number.
times  The wave function is a
mathematical function whose  l is also known as orbital angular
 Heisenberg Uncertainty Principle
value depends upon the momentum or subsidiary
is that it rules out existence of
coordinates of the electron in the quantum number. It defines the
definite paths or trajectories of
atom and does not carry any three dimensional shape of the
electrons and other similar
physical meaning orbital
particles
 Wave functions of hydrogen or  Magnetic orbital quantum
h
 ΔX . ΔP ≥ number.
4 πm hydrogen like species with one
h electron are called atomic orbitals  ml gives information about the
 ΔE . Δt ≥
4π  The probability of finding an spatial orientation of the orbital
 The effect of Heisenberg electron at a point within an atom with respect to standard set of co-
Uncertainty Principle is is proportional to the (ψ 2 ) at ordinate axis.
significant only for motion of that point  2l+1 values of ml are possible
microscopic objects and is
 Quantum mechanical model of  No of orbitals in sub shell- 2l + 1
negligible for that of macroscopic
atom  George Uhlenbeck and Samuel
objects
 Emerges from the application of Goudsmit proposed the presence
 Quantum mechanics was
the Schrödinger equation to atom of the fourth quantum number
developed independently in 1926
 The energy of electrons in atoms known as the electron spin
is quantized quantum number
 STRUCTURE OF ATOM

 The values are +½ or –½. These  Boundary surface diagram for a s  all five 3d orbitals are Equivalent
are called the two spin states of orbital is actually a sphere in energy
the electron and are normally centred on the nucleus  The energy of an electron in a
represented by two arrows, ↑  It encloses a region in which hydrogen atom is determined
(spin up) and ↓ (spin down ) probability of finding the electron solely by the principal quantum
is about 90% number
 An orbital cannot hold more than
two electrons and these two  S orbital spherical and non  1s < 2s = 2p < 3s = 3p = 3d < 4s
electrons should have opposite directional = 4p = 4d = 4f
spins  size of the s orbital increases with  The orbitals having the same
 The orbital wave function or ψ increase in n that is, 4s > 3s > 2s energy are called degenerate
For an electron in an atom has no > 1s  the stability of an electron in
physical meaning  The electron is located further multi-electron atom is because
 Max Born - the square of the away from the nucleus as the total attractive interactions are
wave function ¿ ) at a point gives principal quantum number more than the repulsive
the probability density of the increases interactions
electron at that point  The probability density function  The attractive interactions of an
 1s orbital the probability density is zero on the plane where the electron increases with increase
is maximum at the nucleus and it two lobes touch each other of positive charge (ZE) on the
decreases sharply as we move  P orbital dumbel shape and nucleus
away from it directional  Due to the presence of electrons
 for 2s orbital the probability  The size, shape and energy of the in the inner shells, the electron in
density first decreases sharply to three orbitals are identical the outer shell will not experience
zero and again starts increasing.  They differ however, in the way the full positive charge of the
 The region where this probability the lobes are oriented 2px , 2py , nucleus (ZE)
density function reduces to zero and 2pz  This is known as the shielding of
is called nodal surfaces or simply  the order of the energy and size the outer shell electrons from the
nodes of various p orbitals is 4p > 3p > nucleus by the inner shell
 Number of nodes increases with 2p electrons
increase of principal quantum  radial nodes ( probability density  the net positive charge
number n function is zero) experienced by the outer
 electrons is known as effective
Boundary surface diagrams of  radial nodes = n – l – 1
constant probability density for nuclear charge (ZEFF )
 angular nodes = l
different orbitals give good  Both the attractive and repulsive
 d orbital interactions depend upon the shell
representation of the shapes of
 The five d-orbitals are and shape of the orbital in which
the orbitals
d xy ,d yz , d xz , d x – y , d z
2 2 2 the electron is present
 The shapes of the first four d-
orbitals are similar to each other
 STRUCTURE OF ATOM

 ZEFF experienced by the electron  Only two electrons may exist in  First Excitation state n = 2
decreases with increase of the same orbital and these
azimuthal quantum number electrons must have opposite spin
 The Energy of electrons in s  Hund’s Rule of Maximum
orbital will be lower (more Multiplicity
negative) than that of p orbital  Electrons are first singly
electron which will have less ocuupied and later they pair with
energy than that of d orbital opposite spin
electron  The distribution of electrons into
 the lower the value of (n + l ) for orbitals of an atom is called its
an orbital, the lower is its energy electronic configuration
 If two orbitals have the same  The completely filled and
value of (n + l ), the orbital with completely half filled sub-shells
lower value of n will have the are stable due to
lower energy  Symmetrical distribution of
 energies of the orbitals in the electrons
same subshell decrease with  Exchange Energy
increase in the atomic number  The number of exchanges that
(ZEFF) can take place is maximum when
 The filling of electrons into the the subshell is either half filled or
orbitals of different atoms takes completely filled
place according to the aufbau
 If Exchange energy is maximum ,
principle which is based on the
stability is also maximum
Pauli’s exclusion principle, the
 Extra stability of half-filled and
Hund’s rule
completely filled subshell is due
 aufbau principle
to
 In the ground state of the atoms,
 relatively small shielding
the orbitals are filled in order of
 smaller coulombic repulsion
their increasing energies
energy
 Arrangement of Orbitals with
 Larger exchange energy
Increasing Energy on the Basis of
2
(n + l ) Rule −313.6 Z
 E= 2 Kcal / mol
 Pauli Exclusion Principle n
2
 −13.6 Z
No two electrons in an atom can  E= 2 ev / atom
have the same set of four n
quantum numbers  Angular momentum =
nh h √ l ( l+1 )
=
2π 2π