CHAPTER

02 Structure of Atom
John Dalton 1808: It believed that matter is made up of extremely minute indivisible particles, called atom which take part in chemical
creations.
Atomic Structure: Other important points.
The following are the modified views regarding Dalton’s atomic theory.
(i) Atom is no longer supposed to be indivisible.
(ii) Atoms of some elements may not necessarily possess the same mass.
(iii) Atoms of different elements may possess the same mass.
(iv) Atoms of one element can be transmitted into atoms of other elements.
Dalton’s Hypothesis:
(i) Atoms of same element are alike.
(ii) Atoms of different elements are not alike.
(iii) Compounds are formed when atoms of different elements combine with each other in simple numerical ratio.

1. Composition of Atom
The works of J.J. Thomson and Ernest Rutherford actually laid the foundation of the modern picture of the atom. It is now believed
that the atom consist of several sub-atomic particles like electron, proton, neutron, positron, neutrino, meson etc. Out of these
particles, the electron, proton and the neutron are called fundamental sub atomic particles and others are non-fundamental particles.

Sub –Atomic Particles →

Electron Proton Neutron
Properties ↓
a particle of cathode rays or a particle of anode rays
Component Being neutral was late discovered
-rays. (positive rays/canal rays)
1
Symbol –1 e° H+, p 0 n
Goldstein (1886) &
Discoverer J.J. Thomson (1897) James Chadwick (1932)
Rutherford
Movement straight line straight line do not deviate.
Electric & magnetic field Get deflected Get deflected Do not deflect
e/m ratio 8
–1.76 × 10 coulomb/ gm Less than electron
Formation of the neutron:
Speed Approach speed of light 9 4 12
4 Be + 2 He → 6 C + o n1
ionization power Ionize the gas or
Produce kinetic energy gets B11
+ He 4
→ 7 N 14 + o n1
heating effect 5 2
converted
production of fluorescence Yes yes
neutron is unstable
Produce when fall on heavy
X-ray
metals
1
0n ⎯ ⎯→ 1 H1 + −1 e 0 + 0 0
Penetration power Through metallic sheets neutron Proton electron antineutri no
Depend in nature of gas No Yes
Mass (m) 9.109 × 10 –31
kg 1.673 × 10–27 kg 1.675 × 10–27 kg
Charge(e) – 1.602 × 10–19 C +1.602 × 10–19 C Zero
Specific charge (e/m) –1.76 × 108 C/kg 9.58 × 104 C/kg Zero
Rest mass of electron(m)
(1) According to Einstein's theory of relativity, the mass of electron in motion is, m =
[1 − (u / c) 2 ]
m0
m=
u2
1–
c2
Where u = velocity of the electron, c = velocity of light. = 3 × 108 m/s
(2) The first precise measurement of the charge on the electron was made by Robert A. Millikan in 1909 by oil drop experiment,
(−1.6022 10−19 coulomb)
Page 12 | Structure of Atom Crash Course Chemistry

1.1 Some other fundamental particles

Particle Symbol Nature Discovered by

Positron e+ , +1e0,  + + Anderson (1932)

Neutrino  0 Pauli (1933) and Fermi (1934)
Anti-proton p− – Chamberlain Sugri (1956) and Weighland (1955)

Positive mu meson + + Yukawa (1935)

Negative mu meson − – Anderson (1937)

Positive pi-meson + +
−
Negative pi meson  – Powell (1947)

Neutral pi-meson 0 0

2. Atomic Number and Mass Number

(1) Atomic Number (Z) = Number of positive charge on nucleus = Number of protons in nucleus = Number of electrons in a
neutral atom.
(2) Mass Number (A) = Number of protons or Atomic number (Z) + Number of neutrons
Number of neutrons = A – Z
(3) Atomic Mass= It is the mass of an atom of a chemical element expressed in atomic mass units. It is approximately equivalent
to the number of protons and neutrons in the atom

3. Atomic Species
Atomic
Similarities Differences Examples
species
(1) Atomic No. (Z) (1) Mass No. (A) 1 2 3
(1) 1 H, 1 H, 1 H
(2) No. of protons (2) No. of neutrons 16 17 18
(3) No. of electrons (3) Physical properties (2) 8 O, 8 O, 8 O
Isotopes
(4) Electronic configuration 35 37
(3) 17 Cl, 17 Cl
(5) Chemical properties
(6) Position in the periodic
table
(1) Mass No. (A) (1) Atomic No. (Z) 40 40 40
(1) 18 Ar, 19 K, 20Ca
(2) No. of nucleons (p + n) (2) No. of protons, electrons, and 130 130 130
neutrons (2) 52 Te, 54 Xe, 56 Ba
Isobars (3) Electronic configuration
(4) Chemical properties
(5) Position in the periodic table

No. of neutrons (1) Atomic No. 30 31 32

(1) 14 Si, 15 P, 16 S
(2) Mass No., protons and electrons 39 40
(3) Electronic configuration (2) 19 K, 20Ca
Isotones (4) Physical and chemical properties (3) 3 4
1 H, 2 He
(5) Position in the periodic table
13 14
(4) 6 C, 7 N

(1) No. of electrons At. No., mass No. (1) N2O, CO2, CNO−(22e− )
(2) Electronic configuration
Isoelectro- (2) CO, CN−, N2(14e−)
nic
species
(3) H−, He, Li+, Be2+(2e−)
(4) P3−, S2−, Cl −, Ar, K+andCa2+(18e−)

Determination of isotopic mass :

 % of A x x  y
y
   % of A  A x and A y is the isotope of the element A .
 100  mass of A  +  100  mass of A  where
   
Crash Course Chemistry Structure of Atom | Page 13

4. Electromagnetic Radiations
Light and other forms of radiant energy propagate without any medium in the space in the form of waves are known as
electromagnetic radiations. These waves can be produced by a charged body moving in a magnetic field or a magnet in an electric
field. e.g. X-rays,  − rays, cosmic rays, ordinary light rays etc.

4.1 Characteristics
All electromagnetic radiations travel with the velocity of light.
These consist of electric and magnetic fields components that oscillate in directions perpendicular to each other and perpendicular
to the direction in which the wave is traveling.
(1) Wavelength : The distance between two nearest crests or nearest troughs is called the wavelength. It is denoted by
λ(lambda) and is measured is terms of centimetre (cm), angstrom (Å), micron(µ) or nanometre (nm).
(2) Frequency : It is defined as the number of waves which pass through a point in one second. It is denoted by the
symbol and is expressed in terms of cycles (or waves) per second (cps) or hertz (Hz).
v = c/
(3) Velocity : It is defined as the distance covered in one second by the wave. It is denoted by the letter ‘c’.
c = v
(4) Wave number : This is the reciprocal of wavelength, i.e., the number of wavelengths per centimetre.
v = 1/ 
(5) Time period : Time taken by the wave for one complete cycle or vibration is called time period. It is denoted by T
expressed in terms of second (s)
T = 1/v
(6) Amplitude : It is defined as the height of the crest or depth of the trough of a wave. It is denoted by the letter ‘A’. It
determines the intensity of the radiation.

5. Spectrum
5.1 Emission Spectrum and Absorption Spectrum

Emission Spectrum Absorption Spectrum

Continuous Spectrum : Discontinuous Spectrum : Absorption spectrum depicts the

wavelengths absorbed by a species. The
When white light from When some wavelengths are missing from the
wavelengths absorbed appear as lines
any source is analyzed spectrum, it is called discontinuous spectrum.
missing from the continuous spectrum of
by passing through a
radiation to which species is exposed.
prism, it splits up into Line Spectrum : Band Spectrum : Each spectral line is characteristic of one
colors from violet to
Spectrum containing Band spectrum is the electron transition from lower to higher
red. Each of these
few lines, separated name given to groups of energy level. (Discontinuous spectrum)
colors is so continuous
that this merges into from each other by lines so closely spaced
the next. dark spaces. Also that each group appears
called atomic to be a band. It is
VIBGYOR spectrum produced by multi-
atomic species or
molecules.

5.2 Hydrogen Spectrum

Is a line emission spectrum or atomic emission spectrum or discontinuous spectrum. To evaluate wavelength of various H-lines
1  1 1
= = = R 2 − 2
 c  n1 n2 
Where R is universal constant known as Rydberg’s constant its value is 109, 678 cm −1 or R.

6. Planck Quantum Theory

When a black body is heated, it emits thermal radiations of different wavelengths or frequency. The radiant energy which is emitted
or absorbed by the black body is not continuous but discontinuous in the form of small discrete packets of energy, each such packet
of energy is called a 'quantum'. In the case of light, the quantum of energy is called a 'photon'.
Page 14 | Structure of Atom Crash Course Chemistry

The energy of each quantum is directly proportional to the frequency (  ) of the radiation, i.e.
hc c
E   E = h = =
 
−34
Where, h = Planck's constant = 6.62×10 erg-sec. or 6.62  10 Joules − sec .
–27

The total amount of energy emitted or absorbed by a body will be some whole number quanta.
Hence E = nh , where n is an integer no of photons.

7. Photoelectric Effect

When radiations with certain minimum frequency (0 ) strike the surface of a metal, the electrons are ejected from the surface of the
metal. This phenomenon is called photoelectric effect and the electrons emitted are called photo-electrons.
The current constituted by photoelectrons is known as photoelectric current.
(1) The electrons are ejected only if the radiation striking the surface of the metal has at least a

Number of electrons
minimum frequency ( 0 ) called Threshold frequency. The minimum potential at which the Higher intensity
light
plate photoelectric current becomes zero is called stopping potential.

ejected
(2) The velocity or kinetic energy of the electron ejected depend upon the frequency of the Lower intensity
incident radiation and is independent of its intensity. light
(3) The number of photoelectrons ejected is proportional to the intensity of incident radiation.
(4) Einstein’s photoelectric effect equation Frequency

KE = h – h 0 Fig. 2.1
1 2 1 1 
mvmax = h − h 0 = hc  − 
2   0 
 0 and 0 are threshold frequency and threshold wavelength.

8. Atomic Models
8.1 Thomson Model
(1) Atom is a positively charged sphere having electrons embedded uniformly giving an overall picture of plum pudding or
raisin pudding or watermelon model.
(2) This model failed to explain the line spectrum of an element and the scattering experiment of Rutherford
8.2 Rutherford Model
Rutherford carried out an experiment on the bombardment of thin (10–4 mm) Gold foil with high speed positively charged
 − particles emitted from Radium
Observation:
(1) The nucleus which is small in size but carries the entire mass i.e. contains all the neutrons and protons.
(2) The extranuclear part which contains electrons.
Note : This is also called ‘Planetary atomic model.
Properties of the nucleus
(1) The nucleus is a small, heavy, positively charged portion of the atom and located at the centre of the atom.
(2) The nucleus contains neutrons and protons, and hence these particles collectively are also referred to as nucleons.
(3) The radius of the nucleus is of the order of 1.5 10−15 m to 6.5 10−15 m i.e. 1.5 to 6.5 Fermi.
(4) The radius of the nucleus ( rn ) is given by the following relation,

rn = ro (= 1.25 10−15 m)  A1/3

(5) The volume of the nucleus is 10 −15 times that of an atom.
Drawbacks of Rutherford model
(1) If an electron radiate energy during revolution, it should also continuously lose its energy and should set up spiral
motion ultimately falling into the nucleus.
(2) It could not explain the line spectra of H − atom and discontinuous spectrum nature.
Crash Course Chemistry Structure of Atom | Page 15

8.3 Bohr Atomic Model: Postulates of Bohr Atomic Model

(1) An atom consists of positively charged nucleus responsible for almost entire mass of the atom.
(2) The electrons revolve around the nucleus in certain permitted circular orbits of definite radii.
(3) The permitted orbits are those for which the angular momentum of an electron is an integral multiple of h / 2
nh
L = mvr = ; n = 1 , 2, 3, …… 
2
[This equation is known as the Bohr quantization postulate.]
Bohr’s theory satisfactorily explains the spectra of species having one electron, viz. hydrogen atom, He + , Li 2+ etc.
Mathematical Equations
Calculation of radius of
 n2
Bohr’s orbit rn =  0.529Å
Z
Calculation of velocity of an
 2.188  108 Z
Vn = cm. sec−1
electron n
Total energy of electron = K.E. + P.E. of electron
kZe2 kZe2 kZe2
= − =−
2r r 2r

Z2
Calculation of energy of an E = −21.8  10−12  erg per atom
 n2
electron in Bohr's orbit
Z2
= −21.8  10−19  J per atom(1J = 107 erg)
n2

Z2
E = −13.6  eV per atom (1eV = 1.6  10–19 J )
n2

NOTE: The negative sign in the above equations of energy shows that the electron and nucleus form a bound system, i.e. the
electron is attracted towards the nucleus. Thus, if an electron is to be taken away from the nucleus, energy has to be supplied.
The energy of the electron in n = 1 orbit is called the ground state energy; that in the n = 2 orbit is called the first excited state
energy, etc. When n =  then E = 0 which corresponds to ionized atom i.e. the electron and nucleus are infinitely separated
H → H+ + e− (ionization).
When an electron jumps from an outer orbit (higher energy) n2 to an inner orbit (lower energy) n1, then the wavelength of
emitted radiation is given by
1 1 1
=  = RZ 2  2 − 2 
  n1 n2 
2 2k 2me4
Where R = R is known as Rydberg constant. Its value to be used is 109678 cm−1.
ch3

Hydrogen Spectrum

Transition max n2
S.N. Spectral series Lies in the region = 2 2 2
n2  n1 min n2 − n1
(1) Lyman series Ultraviolet region n1 = 1 4
n2 = 2, 3, 4.... 3
(2) Balmer series Visible region n1 = 2 9
n2 = 3, 4,5.... 5
(3) Paschen series Infrared region n1 = 3 16
n2 = 4,5,6.... 7
Page 16 | Structure of Atom Crash Course Chemistry

(4) Brackett series Infrared region n1 = 4 25

n2 = 5,6,7.... 9
(5) Pfund series Infrared region n1 = 5 36
n2 = 6,7,8.... 11
(6) Humphrey series Far infrared region n1 = 6 49
n2 = 7,8.... 13

Limitations
(1) Bohr theory was very successful in predicting and accounting the energies of line spectra of hydrogen i.e. one electron
system, could not explain the presence of multiple spectral lines.
(2) could not explain the splitting of spectral lines in a magnetic field (Zeeman effect) and an electric field (Stark effect).
(3) unable to explain the dual nature of matter as explained on the basis of de Broglie's concept.
(4) could not explain uncertainty principle.
(5) No conclusion was given for the concept of quantization of energy.
8.4 Bohr-Sommerfeld Model
(1) Sommerfeld, in 1915 proposed that the moving electron might describe elliptical orbits in addition to circular orbits and
nucleus is situated at one of the foci.
(2) In an elliptical motion, both the angles of revolution and the distance of the electron from the nucleus changes.
(3) The distance from the nucleus is termed as radius vector and the angle of revolution is known as an azimuthal angle.
(4) The tangential velocity of the electron at a particular instant can be resolved into two components, one along the radius
vector called radial velocity and the other perpendicular to radius vector called transverse or angular velocity.
h
Radial momentum = n
2
h
Azimuthal momentum = n
2
n Lenght of major axis
nr and n are related to main orbit ‘n' as n = nr + n or =
n length of the minor axis

9. Dual Nature of Electron

9.1 de-Broglie Equation
According to de-Broglie, the wavelength associated with a particle of mass m, moving with velocity  is given by the relation
h
=
mv
h = Planck’s constant = 6.626 × 10–34 Js

Derivation
hc  c
According to Planck's equation, E = h =   = 
  
(1) The energy of the photon (on the basis of Einstein's mass-energy relationship), E = mc 2
hc h
(2) Equating both = mc 2 or  = which is same as a de-Broglie relation. ( mc = momentum)
 mc
(3) This was experimentally verified by Davisson and Germer by observing the diffraction effects with an electron beam.
Let the electron be accelerated with a potential of V then the Kinetic energy is
1
mv 2 = eV
2
Multiply both side by 'm'
1 2 2
m v = eVm ; m 2v 2 = 2eVm
2
mv = 2eVm = P
h
 =
2eVm
Crash Course Chemistry Structure of Atom | Page 17

(4) If Bohr's theory is associated with de Broglie's equation then the wavelength of an electron can be determined in Bohr's
orbit and relate it with circumference and multiply with a whole number

2 r h
2 r = n or  = From the de-Broglie equation,  =
n mv

h 2 r nh n = 1,2,3,4,....
Thus = or mvr =
mv n 2 n  1  5,2  5,3  5,...

(5) The de-Broglie equation is applicable to all material objects but it has significance only in the case of microscopic
particles. Since we come across macroscopic objects in our everyday life, the de-Broglie relationship has no significance
in everyday life.

10. Heisenberg Uncertainty Principle

(1) This principle states “It is impossible to specify at any given moment both the position and momentum (velocity) of an
electron”.

h
x . p  [Where x = uncertainty in the position of the particle, p = uncertainty in the momentum of the particle ]
4

h
Now since p = m v x v  x v =uncertainty product
4 m

h
x. mv  or
4

h
(2) In terms of uncertainty in energy, E and uncertainty in time t, this principle is written as, E . t 
4

11. Schrodinger Wave Equation

11.1 Significance of  and 2
In it, the electron is described as a three-dimensional wave in the electric field of a positively charged nucleus.

 2   2   2  8 2m 82 m
+ + + (E − V )  = 0 2 + (E– V) = 0
x 2 y 2 z 2 h2 n2

Where x, y and z are the 3 space coordinates, m = mass of the electron, h = Planck's constant, E = Total energy, V = potential
energy of electron,  = amplitude of wave also called a wave function,  = for an infinitesimal change.

Physical significance of  and 2

(1) The wave function  represents the amplitude of the electron wave. The amplitude  is thus a function of space
coordinates and time i.e.  = (x,y, z....times) and describes atomic orbitals.

(2) For a single particle, the square of the wave function ( 2 ) is proportional to the probability of finding that particle in
that region.

 2 = significant value

(3) If  2 is maximum then the probability of finding e − is maximum around the nucleus, It is the place where the
probability of finding e − is maximum is called electron density, electron cloud or an atomic orbital.
Page 18 | Structure of Atom Crash Course Chemistry

12. Quantum Numbers

The solution of Schrodinger wave equation provides a set of the number called quantum number.

Principal Quantum Azimuthal Quantum Magnetic Quantum - Spin Quantum Number

Number (n) - BOHR Number (l) - Number (m) – LINDE (s) - UHLENBECK &
SOMMERFELD Goudsmit

It determines the average It determines the number of It gives the number of a The value of ‘s’ is +1/2 and
distance between the electron subshells or sublevels to permitted orientation of –1/2, which signifies the spin or
and nucleus, means it which the electron belongs subshells. rotation or direction of an
denotes the size of an atom. and about the shape of electron on its axis during
The value of m varies from –l
subshells. movement.
to +l through zero.
= 0 to (n – 1)

It determines the energy of It also expresses the energies It tells about the splitting of The spin may be clockwise or
the electron in an orbit where of subshells s  p  d  f spectral lines in the magnetic anticlockwise.
the electron is present. (increasing energy). field i.e. this quantum number
It represents the value of spin
proves the Zeeman effect.
angular momentum is equal to
h
No energy shell in atoms of The value of l = 0 to (n − 1) For a given value of ‘l’ the s(s + 1).
known elements possesses total value of ‘m’ is equal to 2
always. Where ‘n' is the
more than 32 electrons. number of principal shells. (2l + 1).
It gives the information of represents the orbital angular
orbit K, L, M, N…………. momentum which is equal to
h
l(l + 1)
2

The maximum number of The maximum number of For a given value of ‘n' the The maximum spin of an atom
electrons in an orbit electrons in the subshell total value of 'm' is equal to S = 1 / 2  number of unpaired
represented by this quantum = 2(2l + 1) = 4 + 2 n2. electrons.
number is 2n 2 .

13. Shape of Orbitals

Shape of ‘s’ Orbital Shape of ‘p’ Orbitals Shape of' ‘d’ Orbitals Shape of ‘f’ Orbitals

l=0 and m=0 l=1, and m=+1,0,–1 l =2 l=3

so ‘s’ orbital have only one means there are three ‘p’ ‘m’ = –2, –1, 0, +1, +2. It ‘m’ are –3, –2, –
unidirectional orientation i.e. orbitals, which is symbolized shows that the ‘d’ orbitals has 1,0,+1,+2,+3. It shows that
the probability of finding the as p x , py , p z . five orbitals as the ‘f’ orbitals have seven
electrons is the same in all d xy , dyz , dzx , d x 2 −y2 , dz 2 . orientations.
directions.

The size and energy of ‘s’ Shape of ‘p' orbital is a The shape of the d orbital is a The ‘f’ orbital is complicated
orbital with increasing ‘n’ will dumb bell in which the two double but shape of dz2 is dumb in shape
be 1s  2s  3s  4s. lobes on an opposite side bell shape.
separated by the nodal
It has directional properties.
plane.
There is no radial node for 1s Each ‘d’ orbital is identical in
p-orbital has directional
orbital since it is starting from shape, size, and energy but dz2
properties
the nucleus is exceptional
Degenerate orbital.
It is know as degeneracy.
Crash Course Chemistry Structure of Atom | Page 19

14. Node and Nodal Plane

(i) Node and Nodal Plane - represents the region where the probability of finding an electron is zero (i.e.  and  2 = 0).
Similarly, the nodal plane represents the plane having zero probability of finding an electron.
(ii) Nodes are of two types:
(a) Radial node: A radial node is a spherical region around the nucleus having  and  2 equals to zero.
Radial nodes = n − l − 1
(b) Angular node: The plane in which probability density function is zero, is called a nodal plane or angular node.
Angular nodes = l
Total nodes = radial nodes + angular nodes = n − 1
n and l are principal and azimuthal quantum numbers respectively.

15. Rules for Filling of Electrons in Various Orbitals

(1) Aufbau’s Principle : Electrons are added one by one to the various orbitals in order of their increasing energy starting with
the orbital of lowest energy. The increasing order of energy of various orbitals is:
1s  2s  2 p  3s  3 p  4 s  3d  4 p  5s  4d  5 p  6s  4 f  5d  6 p  7s  5 f  6d  7 p.........
(2) (n+l) Rule: In neutral isolated atom, lower the value of (n +l) for an orbital, lower is its energy.
However, if two different types of orbitals have the same value of (n + l), the orbitals with a lower value of n has lower energy.
(3) Pauli’s Exclusion Principle : According to this principle ,no two electrons in an atom will have the same value of all the
four quantum numbers". If one electron in an atom has the quantum numbers n = 1, l = 0 , m = 0 and s = +1 / 2 , no other
electron can have the same four quantum numbers.
Page 20 | Structure of Atom Crash Course Chemistry

(4) Hund’s Rule : This rule deals with the filling of electrons in the orbitals having equal energy (degenerate orbitals).
According to this rule, “Electron pairing in p, d and f orbitals cannot occur until each orbital of a given subshell contain one
electron each or is singly occupied".

16. Electronic Configuration of Elements

Usually the electronic configuration of the atom of any element is simply represented by the notations.

16.1 Some of the exceptions

Cu – (Z = 29) expected electronic configuration is 1s2 2s2 2p6 3s2 3p6 4s2 3d9 unstable but in 1s
2 2 6 2 6 1 10
reality the configuration is 1s 2s 2p 3s 3 p 4 s 3d (stable). 2s 2p

Cr – (Z = 24 ) expected the configuration 1s 2 2s 2 2p 6 3s 2 3 p 6 4 s 2 3d 4 unstable reality 3s 3p 3d

2 2 6 2 6 1 5
configuration of 1s 2s 2p 3s 3 p 4 s 3d (stable) 4s 4p 4d 4f

16.2 The factor responsible for this is the extra stability of half-filled and completely 5s 5p 5d 5f
filled orbital
6s 6p 6d
(1) Exchange energy
(2) Symmetrical distribution. 7s 7p