Structure of Atom

Chapter
Erwin Schrödinger
2

CONTENTS
2.1 Composition of atom

2.2 Atomic number, Mass number and Atomic species

2.3 Electromagnetic radiation’s

2.4 Atomic spectrum- Hydrogen spectrum

2.5 Thomson's model

2.6 Rutherford's nuclear model

2.7 Planck's Quantum theory and Photoelectric effect

2.8 Bohr’s atomic model

2.9 Bohr – Sommerfeld’s model

2.10 Dual nature of electron

2.11 Heisenberg’s uncertainty principle

2.12 Schrödinger wave equation

Science has produced a microscopic
structure of the atom, but it’s structure is so
2.13 Quantum numbers and Shapes of orbitals detailed and so subtle of something which is
far removed from our immediate experience
2.14 Electronic configuration principles that it is difficult to see how many of its
features were constructed. Yet among all the
2.15 Electronic configurations of elements experiments used to form the theory of atomic
structure, there stand a few which have been
Assignment (Basic and Advance Level) most in-fluential in shaping its major
features.
Answer Sheet of Assignment
Structure of Atom

1. John Dalton 1808, believed that matter is made up of extremely minute indivisible particles, called atom which
can takes part in chemical reactions.
2. These can neither be created nor be destroyed.
3. However, modern researches have conclusively proved that atom is no longer an indivisible particle.
4. Modern structure of atom is based on Rutherford’s scattering experiment on atoms and on the concepts of
quantization of energy.

Composition of atom.
1. It is now believed that the atom consists of several sub-atomic particles like electron, proton, neutron, positron,
neutrino, meson etc.
2. Out of these particles, the electron, proton and the neutron are called fundamental subatomic particles and others
are non-fundamental particles.

Electron (–1eo)
(1) It was discovered by J.J. Thomson (1897) and is negatively charged particle.
Electron is a component particle of cathode rays.
(2) Cathode rays were discovered by William Crooke's & J.J. Thomson (1880) using a cylindrical hard
glass tube fitted with two metallic electrodes. The tube has a side tube with a stop cock. This tube was known as
discharge tube. They passed electricity (10,000V) through a discharge tube at very low pressure ( 10 2 to
10 3 mm Hg ) . Blue rays were emerged from the cathode. These rays were termed as Cathode rays.

Cathode rays Gas at low

pressure TC Vaccum pump
Cathode Anode

High voltage
– +

Discharge tube experiment for production of cathode rays

 Structure of Atom

(3) Properties of Cathode rays

(i) Cathode rays travel in straight line.
(ii) Cathode rays produce mechanical effect, as they can rotate the wheel placed in their path.
(iii) Cathode rays consist of negatively charged particles known as electron.
(iv) Cathode rays travel with high speed approaching that of light (ranging between 10 9 to 10 11 cm/sec)
(v) Cathode rays can cause fluorescence.
(vi) Cathode rays heat the object on which they fall due to transfer of kinetic energy to the object.
(vii) When cathode rays fall on solids such as Cu, X  rays are produced.

(viii) Cathode rays possess ionizing power i.e., they ionize the gas through which they pass.
(ix) The cathode rays produce scintillation the photographic plates.
(x) They can penetrate through thin metallic sheets.
(xi) The nature of these rays does not depend upon the nature of gas or the cathode material used in
discharge tube.
(xii) The e/m (charge to mass ratio) for cathode rays was found to be the same as that for an e 
(1.76  10 8 coloumb per gm). Thus, the cathode rays are a stream of electrons.

(4) R.S. Mullikan measured the charge on an electron by oil drop experiment.
The charge on each electron is  1.602  10 19 C.

(5) Name of electron was suggested by J.S. Stoney.

The specific charge (e/m) on electron was first determined by J.J. Thomson.

(6) Rest mass of electron is 9.1  1028 gm  0.000549amu  1 / 1837 of the mass of hydrogen atom.

Rest mass of electron(m )

(7) According to Einstein’s theory of relativity, mass of electron in motion is, m 
[1  (u / c) 2 ]
Where u = velocity of electron, c= velocity of light.
When u=c than mass of moving electron =.

(8) Molar mass of electron = Mass of electron × Avogadro number = 5.483  10 4 .

(9) 1.1  10 27 electrons =1gram.

Structure of Atom

(10) 1 mole electron = 0.5483 mili gram.

(11) Energy of free electron is ≈ 0. The minus sign on the electron in an orbit, represents attraction between
the positively charged nucleus and negatively charged electron.

(12) Electron is universal component of matter and takes part in chemical combinations.

(13) The physical and chemical properties of an element depend upon the distribution of electrons in outer shells.

(14) The radius of electron is 4.28  10 12 cm.

(15) The density of the electron is = 2.17  10 17 g / mL .

Proton (1H1, H+, P)

(1) Proton was discovered by Goldstein and is positively charged particle.

It is a component particle of anode rays.
(2) Goldstein (1886) used perforated cathode in the discharge tube and repeated Thomson's experiment
and observed the formation of anode rays. These rays also termed as positive or canal rays.

Cathode rays
Anode rays
TC Vaccum pump

Perforated High voltage

cathode – +

Perforated tube experiment for production of anode rays

(3) Properties of anode rays

(i) Anode rays travel in straight line.
(ii) Anode rays are material particles.
(iii) Anode rays are positively charged.
 Structure of Atom

(iv) Anode rays may get deflected by external magnetic field.

(v) Anode rays also affect the photographic plate.
(vi) The e/m ratio of these rays is smaller than that of electrons.
(vii) Unlike cathode rays, their e/m value is dependent upon the nature of the gas taken in the tube.
It is maximum when gas present in the tube is hydrogen.
(viii) These rays produce flashes of light on ZnS screen.

(4) Charge on proton = 1.602  10 19 coulombs = 4.80  10 10 e.s. u.

(5) Mass of proton = Mass of hydrogen atom= 1.00728amu  1.673  10 24 gram  1837 of the mass of electron.

(6) Molar mass of proton = mass of proton  Avogadro number  1.008 (approx).

(7) Proton is ionized hydrogen atom (H  ) i.e., hydrogen atom minus electron is proton.

(8) Proton is present in the nucleus of the atom and it's number is equal to the number of electron.
(9) Mass of 1 mole of protons is  1.007 gram.
(10) Charge on 1 mole of protons is  96500 coulombs.
4 3
(11) The volume of a proton (volume = r ) is  1.5  10 38 cm3 .
3

(12) Specific charge of a proton is 9.58  10 4 Coulomb/gram.

Neutron (on1, N)
(1) Neutron was discovered by James Chadwick (1932) according to the following nuclear reaction,

4 Be 9  2 He 4  6 C12  o n1 or 5 B11  2 He 4  7 N 14  o n1

(2) The reason for the late discovery of neutron was its neutral nature.
(3) Neutron is slightly heavier (0.18%) than proton.
(4) Mass of neutron = 1.675  10 24 gram = 1.675  10 27 kg = 1.00899 amu  mass of hydrogen atom.
(5) Specific charge of a neutron is zero.
(6) Density = 1.5  10 14 gram / c.c.
(7) 1 mole of neutrons is  1.008 gram.
(8) Neutron is heaviest among all the fundamental particles present in an atom.
(9) Neutron is an unstable particle. It decays as follows :
1
0n  1 H1  1 e 
0
0 0

neutron proton electron anti nutrino

(10) Neutron is fundamental particle of all the atomic nucleus, except hydrogen or protium.
Structure of Atom

Comparison of mass, charge and specific charge of electron, proton and neutron
Name of constant Unit Electron(e–) Proton(p+) Neutron(n)
amu 0.000546 1.00728 1.00899
Mass (m) kg 9.109 × 10 –31
1.673 × 10 –27
1.675 × 10–24
Relative 1/1837 1 1
Coulomb (C) – 1.602 × 10–19 +1.602 × 10–19 Zero
Charge(e) esu – 4.8 × 10–10 +4.8 × 10–10 Zero
Relative –1 +1 Zero
Specific charge (e/m) C/g 1.76 × 10 8
9.58 × 10 4
Zero
 The atomic mass unit (amu) is 1/12 of the mass of an individual atom of 6 C 12 , i.e. 1.660  10 27 kg .

Other non fundamental particles

Particle Symbol Nature Charge esu Mass Discovered by
10 –10
(amu)
Positron e  , 1e 0 ,   + + 4.8029 0.0005486 Anderson (1932)

Neutrino  0 0 < 0.00002 Pauli (1933) and Fermi (1934)

Anti-proton p – – 4.8029 1.00787 Chamberlain Sugri (1956) and
Weighland (1955)
Positive mu meson  + + 4.8029 0.1152 Yukawa (1935)

Negative mu meson  – – 4.8029 0.1152 Anderson (1937)

Positive pi meson  + + 4.8029 0.1514

Negative pi meson  – – 4.8029 0.1514 Powell (1947)
Neutral pi meson 0 0 0 0.1454

Atomic number, Mass number and Atomic species.

(1) Atomic number or Nuclear charge

(i) The number of protons present in the nucleus of the atom is called atomic number (Z).
(ii) It was determined by Moseley as,
  a(Z  b) or aZ  ab
where,   X  rays frequency
 s 1
Z= atomic number of the metal
Z
a & b are constant.
(iii) Atomic number = Number of positive charge on nucleus = Number of protons in nucleus = Number
of electrons in nutral atom.
(iv) Two different elements can never have identical atomic number.
 Structure of Atom

(2) Mass number

(i) The sum of proton and neutrons present in the nucleus is called mass number.
Mass number (A) = Number of protons + Number of neutrons or Atomic number (Z)
or Number of neutrons = A – Z .
(ii) Since mass of a proton or a neutron is not a whole number (on atomic weight scale), weight is not
necessarily a whole number.
(iii) The atom of an element X having mass number (A) and atomic number (Z) may be represented by a
symbol,
Element Mass number
A
Atomic number
Z X
e.g. 9 F 19 , 8 O16 , 7 N 14 etc.

Note :  Negative ion is formed by gaining electrons and positive ion by the loss of electrons.

 Number of lost or gained electrons in positive or negative ion =Number of protons  charge on ion.

(3) Different Types of Atomic Species

Atomic species Similarities Differences Examples

(i) Atomic No. (Z) (i) Mass No. (A) (i) 11 H, 12 H, 13 H
(ii) No. of protons (ii) No. of neutrons 16 17 18
(ii) 8 O, 8 O, 8 O
(iii) No. of electrons (iii) Physical properties
Isotopes (iii) 35 37
17 Cl, 17 Cl
(iv) Electronic configuration
(Soddy)
(v) Chemical properties
(vi) Position in the periodic
table
(i) Mass No. (A) (i) Atomic No. (Z) (i) 40
18
40
Ar, 19 K, 40
20 Ca

(ii) No. of nucleons (ii) No. of protons, electrons 130 130 130
(ii) 52 Te, 54 Xe, 56 Ba
and neutrons
Isobars (iii)Electronic configuration
(iv) Chemical properties
(v) Position in the perodic
table.
Structure of Atom

(i) Atomic No. (i) 30

14
31
Si, 15 32
P, 16 S
(ii) Mass No., protons and 39
(ii) 19 K, 40
20 Ca
electrons.
(iii) Electronic configuration (iii) 13 H, 42 He
Isotones No. of neutrons
13 14
(iv) Physical and chemical (iv) 6 C, 7 N
properties
(v) Position in the periodic
table.
Isotopic No. (i) At No., mass No., (i) 92 U 235 , 90 Th231
(N – Z) or (A – 2Z) electrons, protons, neutrons.
Isodiaphers (ii) 19 K 39 , 9 F 19
(ii) Physical and chemical
properties. (iii) 29 Cu 65 , 24 Cr 55

(i) No. of electrons At. No., mass No. (i) N 2 O, CO2 , CNO (22e  )
(ii) Electronic configuration
Isoelectronic (ii) CO, CN  , N 2 (14e  )
species (iii) H  , He, Li  , Be 2 (2e  )
(iv) P 3  , S2 , Cl  , Ar, K and Ca2 (18e  )

(i) No. of atoms (i) N 2 and CO

(ii) No. of electrons (ii) CO2 and N 2 O
(iii) Same physical and
Isosters (iii) HCl and F2
chemical properties.
(iv) CaO and MgS

(v) C6 H 6 and B3 N 3 H 6

A
ZX Examples based on Atomic number, Mass number and Atomic species

Example : 1 Nitrogen atom has an atomic number of 7 and oxygen has an atomic number of 8. The total number of
electrons in a nitrate ion is
(a) 30 (b) 35 (c) 32 (d) None
Solution : (c) Number of electrons in an element = Its atomic number
So number of electrons in N=7 and number of electrons in O=8.
Formula of nitrate ion is NO 3

So, in it number of electrons

 1  number of electrons of nitrogen 3  number of electrons of oxygen +1 (due to negative charge)
 1  7  3  8  1  32
 Structure of Atom

Example :2 An atom of an element contains 11 electrons. Its nucleus has 13 neutrons. Find out the atomic number and
approximate atomic weight.
(a) 11, 25 (b) 12, 34 (c) 10, 25 (d) 11, 24
Solution : (d) Number of electrons =11
 Number of protons = Number of electron =11
Number of neutrons = 13
Atomic number of element = Number of proton = Number of electrons =11
Further, Atomic weight = Number of protons + Number of neutrons =11 + 13=24

31 40 108
Example : 3 How many protons, neutrons and electrons are present in (a) 15 P (b) 18 Ar (c) 47 Ag ?

Solution : The atomic number subscript gives the number of positive nuclear charges or protons. The neutral atom
contains an equal number of negative electrons. The remainder of the mass is supplied by neutrons.

Atom Protons Electrons Neutrons

31
15 P 15 15 31 – 15=16

40
18 Ar 18 18 40 – 18=22

108
47 Ag 47 47 108 – 47=61

Example :4 State the number of protons, neutrons and electrons in C 12 and C14 .

Solution : The atomic number of C 12 is 6. So in it number of electrons = 6

Number of protons =6; Number of neutrons =12 – 6=6

The atomic number of C 14 is 6. So in it number of electrons = 6

Number of protons = 6; Number of neutrons =14 – 6=8

Example :5 Predict the number of electrons, protons and neutrons in the two isotopes of magnesium with atomic number 12
and atomic weights 24 and 26.

Solution : Isotope of the atomic weight 24, i.e. 12 Mg 24 . We know that

Number of protons = Number of electrons =12

Further, Number of neutrons = Atomic weight – Atomic number =24 – 12 =12

Similarly, In isotope of the atomic weight 26, i.e. 12 Mg 26

Number of protons = Number of electrons =12

Number of neutrons = 26 – 12 = 14
Structure of Atom

Electromagnetic Radiations.

(1) Light and other forms of radiant energy propagate without any medium in the space in the form of waves
are known as electromagnetic radiations.
(2) These waves can be produced by a charged body moving in a magnetic field or a magnet in a electric field.
e.g.   rays,   rays, cosmic rays, ordinary light rays etc.

Characteristics :
(i) All electromagnetic radiations travel with the velocity of light.
(ii) 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 travelling.

(3) Five characteristics of waves :

(i) Wavelength : The distance between two

Crest
nearest crests or nearest troughs is called the Wavelength

wavelength. It is denoted by  (lambda) and Vibrating

source
is measured is terms of centimeter(cm), Energy
angstrom(Å), micron(  ) or nanometre (nm).

1Å  10 8 cm  10 10 m
Trough
1  10 4 cm  10 6 m

1nm  10 7 cm  10 9 m
1cm  10 8 Å  10 4   10 7 nm

(ii) Frequency : It is defined as the number of waves which pass through a point in one second. It is denoted
by the symbol  (nu) and is expressed in terms of cycles (or waves) per second (cps) or hertz (Hz).
  distance travelled in one second = velocity =c
c



(iii) Velocity : It is defined as the distance covered in one second by the wave. It is denoted by the letter ‘c’.
All electromagnetic waves travel with the same velocity, i.e., 3  1010 cm / sec .
c    3  1010 cm / sec
Thus, a wave of higher frequency has a shorter wavelength while a wave of lower frequency has a
longer wavelength.
 Structure of Atom

(iv) Wave number : This is the reciprocal of wavelength, i.e., the number of wavelengths per centimetre. It
is denoted by the symbol  (nu bar). It is expressed in cm1 or m1 .
1
 

(v) 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.

Electromagnetic spectrum :
The arrangement of various types of electromagnetic radiations in the order of their increasing or
decreasing wavelengths or frequencies is known as electromagnetic spectrum.

Name Wavelength (Å) Frequency (Hz) Source

Radio wave 3  1014  3  107 1  10 5  1  10 9 Alternating current of high
frequency
Microwave 3  107  6  10 6 1  10 9  5  1011 Klystron tube

Infrared (IR) 6  10 6  7600 5  1011  3.95  1016 Incandescent objects

Visible 7600  3800 3.95  1016  7.9  1014 Electric bulbs, sun rays

Ultraviolet (UV) 3800  150 7.9  1014  2  1016 Sun rays, arc lamps with mercury
vapours
X-Rays 150  0.1 2  1016  3  1019 Cathode rays striking metal plate

  Rays 0.1  0.01 3  1019  3  10 20 Secondary effect of radioactive

decay
Cosmic Rays 0.01- zero 3  10 20  infinity Outer space

Atomic spectrum - Hydrogen spectrum.

Atomic spectrum
Spectrum is the impression produced on a photographic film when the radiation (s) of particular wavelength (s) is
(are) analysed through a prism or diffraction grating. It is of two types, emission and absorption.
Type of spectrum :
(1) Emission spectrum : Spectrum produced by the emitted radiation is known as Emission spectrum. This
spectrum corresponds to the radiation emitted ( energy evolved ) when an excited electron returns back to the
ground state.
Emission spectra is of two types,
(i) Continuous spectrum : When sunlight is passed through a prism, it gets dispersed into continuous
bands of different colours. If the light of an incandescent object resolved through prism or
spectroscope, it also gives continuous spectrum of colours.
Structure of Atom

(ii) Line spectrum : If the radiations obtained by the excitation of a substance are analysed with help of a
spectroscope a series of thin bright lines of specific colours are obtained. There is dark space in
between two consecutive lines. This type of spectrum is called line spectrum or atomic spectrum..

(2) Absorption spectrum : Spectrum produced by the absorption radiation is called Absorption spectrum.
or When the white light of an incandescent substance is passed through any substance, this substance
absorbs the radiations of certain wavelength from the white light. On analysing the transmitted light we
obtain a spectrum in which dark lines of specific wavelengths are observed. These lines constitute the
absorption spectrum. The wavelength of the dark lines correspond to the wavelength of light absorbed.

Hydrogen spectrum
(1) Hydrogen spectrum is an example of line emission spectrum or atomic emission spectrum.
(2) When an electric discharge is passed through hydrogen gas at low pressure, a bluish light is emitted.
(3) This light shows discontinuous line spectrum of several isolated sharp lines through prism.
(4) All these lines of H-spectrum have Lyman, Balmer, Paschen, Barckett, Pfund and Humphrey series.
These spectral series were named by the name of scientist discovered them.
(5) To evaluate wavelength of various H-lines Ritz introduced the following expression,
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 .

Thomson's model.
(1) Thomson regarded atom to be composed of positively charged protons and negatively charged electrons.
The two types of particles are equal in number thereby making atom electrically neutral.

(2) He regarded the atom as a positively charged sphere in which negative –

Positively charged
+ + sphere
electrons are uniformly distributed like the seeds in a water melon. – + –
– +
+ Electron
+ –
– +
(3) This model failed to explain the line spectrum of an element and the Positive charge spreaded throughout the sphere

Scattering experiment of Rutherford.

 Structure of Atom

Rutherford's nuclear model.

(1) Rutherford carried out experiment on the bombardment of thin (10–4 mm) Au foil with high speed
positively charged   particles emitted from Ra and gave the following observations, based
on this experiment :

(i) Most of the   particles passed without any deflection.

(ii) Some of them were deflected away from their path.
(iii) Only a few (one in about 10,000) were returned back to their original direction of propagation.
1
(iv) The scattering of   particles  .
4 
sin  
 2
Scattering of  -particle


b
r0 Nucleus

-particle
(energy E eV)

(2) From the above observations he concluded that, an atom consists of

(i) Nucleus which is small in size but carries the entire mass i.e. contains all the neutrons and protons.
(ii) Extra nuclear part which contains electrons. This model was similar to the solar system.
Planetry electron
–
Nucleus
+

10–15 m

10–10 m
Size of the nucleus = 1 Fermi = 10–15 m
Size of the atom 1 Å = 10–10 m

(3) Properties of the Nucleus

(i) Nucleus is a small, heavy, positively charged portion of the atom and located at the centre of the atom.

(ii) All the positive charge of atom (i.e. protons) are present in nucleus.

(iii) Nucleus contains neutrons and protons, and hence these particles collectively are also referred to as nucleons.
Structure of Atom

(iv) The size of nucleus is measured in Fermi (1 Fermi = 10–13 cm).

(v) The radius of nucleus is of the order of 1.5  10 13 cm. to 6.5  10 13 cm. i.e. 1.5 to 6.5 Fermi.
Generally the radius of the nucleus ( rn ) is given by the following relation,

rn  ro ( 1.4  10 13 cm)  A1 / 3

This exhibited that nucleus is 10 5 times small in size as compared to the total size of atom.

(vi) The Volume of the nucleus is about 10 39 cm 3 and that of atom is 10 24 cm3 ,
i.e., volume of the nucleus is 10 15 times that of an atom.

(vii) The density of the nucleus is of the order of 1015 g cm3 or 10 8 tonnes cm 3 or 10 12 kg / cc .
If nucleus is spherical than,
mass of the nucleus mass number
Density = 
volume of the nucleus 4
6.023  10 23  r 3
3

(4) Drawbacks of Rutherford's model

(i) It does not obey the Maxwell theory of electrodynamics, according to it

“A small charged particle moving around an oppositely charged centre continuously loses its energy”.

If an electron does so, it should also continuously lose its energy and should set up spiral motion
ultimately failing into the nucleus.

e–
(ii) It could not explain the line spectra of H  atom
and discontinuous spectrum nature.

Unstability of atom
 Structure of Atom

Planck's Quantum theory and Photoelectric effect

Planck's Quantum theory

(1) Max Planck (1900) to explain the phenomena of 'Black body radiation' and 'Photoelectric effect' gave
quantum theory. This theory extended by Einstein (1905).
(2) If the substance being heated is a black body (which is a perfect absorber and perfect radiator of energy)
the radiation emitted is called black body radiation.

(3) Main points

(i) 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 case of light, the quantum of energy is called a 'photon'.

(ii) The energy of each quantum is directly proportional to the frequency (  ) of the radiation, i.e.
hc
E   or E  h 

where, h  Planck's constant = 6.62×10–27 erg. sec. or 6.62  10 34 Joules sec .

(iii) 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.

(iv) The greater the frequency (i.e. shorter the wavelength) the greater is the energy of the radiation.
E1  1  2
thus,  
E 2  2 1

(v) Also E  E1  E2 , hence,

hc hc hc
 
 1 2
1 1 1
or   .
 1 2
Structure of Atom

hc
E
 Examples based on Planck's Quantum theory

Example: 6 Suppose 10 17 J of energy is needed by the interior of human eye to see an object. How many photons of green
light (  550 nm) are needed to generate this minimum amount of energy
(a) 14 (b) 28 (c) 39 (d) 42
Solution : (b) Let the number of photons required =n
hc 10 17   10 17  550  10 9
n  10 17 ; n    27.6  28 photons
 hc 6.626  10 34  3  10 8

Example: 7 Assuming that a 25 watt bulb emits monochromatic yellow light of wave length 0.57 . The rate of emission of
quanta per sec. will be
(a) 5.89  10 13 sec 1 (b) 7.28  10 17 sec 1 (c) 5  10 10 sec 1 (d) 7.18  10 19 sec 1
Solution: (d) Let n quanta are evolved per sec.
 hc  6.626  10 34  3  10 8
n   25 J sec 1 ; n  25 ; n  7.18  10 19 sec 1

  0.57  10 6

Photoelectric effect
(1) 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.

(2) The electrons are ejected only if the radiation striking the surface of the metal has at least a minimum
frequency ( 0 ) called Threshold frequency.
The minimum potential at which the plate photoelectric current becomes zero is called stopping potential.

(3) The velocity or kinetic energy of the electron ejected depend upon the frequency of the incident radiation
and is independent of its intensity.

(4) The number of photoelectrons ejected is proportional to the intensity of incident radiation.

(5) Einstein’s photoelectric effect equation :

According to Einstein,
Maximum kinetic energy of the ejected electron = absorbed energy – threshold energy

1 1 1 
2
mv max  h  h 0  hc   
2   0 
where,  0 and 0 are threshold frequency and threshold wavelength.
 Structure of Atom

Bohr’s atomic model.

The Bohr postulates :

(1) An atom consists of positively charged nucleus responsible for almost the 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 where h is the Planck’s constant.
If m is the mass and v is the velocity of the
electron in a permitted orbit of radius r, then
nh
L  mvr  ; n  1, 2, 3, …… 
2

Where L is the orbital angular momentum and n is the number of orbit.

The integer n is called the principal quantum number.
This equation is known as the Bohr quantization postulate.

(6) When electrons move in permitted discrete orbits they do not radiate or lose energy.
Such orbits are called stationary or non-radiating orbits.

In this manner, Bohr overcame Rutherford’s difficulty to account for the stability of the atom.
Greater the distance of energy level from the nucleus, the more is the energy associated with it.
The different energy levels were numbered as 1,2,3,4 .. and called as K, L, M, N, …. etc.

(7) Ordinarily an electron continues to move in a particular stationary state or o rbit.

Such a state of atom is called ground state.
When energy is given to the electron it jumps to any higher energy level and is said to be in
the excited state.
When the electron jumps from higher to lower energy state, the energy is radiated.
Structure of Atom

(3) Advantages of Bohr’s theory

(i) Bohr’s theory satisfactorily explains the spectra of species having one electron,

viz. hydrogen atom, He  , Li 2 etc.

(ii) Calculation of radius of Bohr’s orbit :

According to Bohr, radius of orbit in which electron moves is

 h2  n2
r   2 2 .
 4 me k  Z

where, n = Orbit number,


m = Mass number 9.1  10 31 kg ,  
e = Charge on the electron 1.6  10 19 
Z = Atomic number of element, 
k = Coulombic constant 9  10 9 Nm2 c 2 
After putting the values of m,e,k,h, we get.

n2 n2
rn   0.529 Å or rn   0.529nm
Z Z

(a) For a particular system [e.g., H, He+ or Li+2]

r  n 2 [Z = constant]
r1 n12
Thus we have  i.e., r1 : r2 : r3 .......... . :: 1 : 4 : 9....... r1  r2  r3
r2 n22

(b) For particular orbit of different species

1 r Z
r [Z =constant] Considering A and B species, we have A  B
Z rB ZA

Thus, radius of the first orbit H, He  , Li 2 and Be 3 follows the order:

H  He   Li 2  Be 3

(iii) Calculation of velocity of electron

1/ 2
2e 2 ZK  Ze 2 
Vn  , Vn   
nh  mr 

2.188  10 8
For H atom, Vn  cm. sec 1
n
 Structure of Atom

(a) For a particular system [H, He+ or Li+2]

1
V [Z = constant]
n
V1 n2
Thus, we have, 
V2 n1
The order of velocity is V1  V2  V3 ......... or
1 1
V1 : V2 : V3 .......... :: 1 : : ........
2 3

(b) For a particular orbit of different species

V  Z [n =constant]
Thus, we have H  He   Li 2

(c) For H or He+ or Li+2, we have

V1 : V2  2 : 1; V1 : V3  3 : 1; V1 : V4  4 : 1

(iv) Calculation of energy of electron in Bohr’s orbit

Total energy of electron = K.E. + P.E. of electron
kZe 2 kZe 2 kZe 2
  
2r r 2r
 2 2 mZ 2 e 4 k 2
Substituting of r, gives us E 
n2h2
Where, n=1, 2, 3………. 

Putting the value of m, e, k, h,  we get

Z2
E  21.8  10 12  erg per atom
n2
Z2
 21.8  10 19  J per atom (1J  10 7 erg )
n2
Z2
E  13.6  eV per atom (1eV  1.6  10 -19 J )
n2
Z2
 313.6  2 kcal. / mole
n
(1 cal = 4.18J)
 1312 2
= 2
Z kJmol 1
n
Structure of Atom

(a) For a particular system[H, He+ or Li+2]

1
E   2 [Z =constant]
n
E1 n22
Thus, we have 
E 2 n12
The energy increase as the value of n increases

(b) For a particular orbit of different species

E   Z 2 [n =constant]
E A Z A2
Thus, we have  2
EB ZB

For the system H, He+ , Li+2, Be+3 (n-same) the energy order is
H  He   Li 2  Be 3
The energy decreases as the value of atomic number Z increases.

V) When an electron jumps from an outer orbit (higher energy) n 2 to an inner orbit (lower energy) n1 ,
then the energy emitted in form of radiation is given by

E  E n2  E n1
2 2 k 2 me 4 Z 2  1 1 
  2  2 
h2 n 
 1 n2 
 1 1 
 E  13.6Z 2  2  2  eV / atom
 n1 n 2 

As we know that E  h , c   and

1 E
   ,
 hc
2 2 k 2 me 4 Z 2  1 1 
 
ch3  n2  n2 
 1 2 

1  1 1 
This can be represented as    RZ 2  2  2 
  n1 n2 
2 2 k 2 me 4
where, R  R is known as Rydberg constant.
ch3
Its value to be used is 109678cm1 .
 Structure of Atom

(3) Quantization of energy of electron

(i) In ground state :

No energy emission. In ground state energy of atom is minimum and for 1st orbit of H-atom,
n=1.
 E1  13.6eV .

(ii) In excited state :

Energy levels greater than n1 are excited state.
i.e. for H- atom n2 , n3 , n4 are excited state.
For H- atom first excitation state is  n 2

(iii) Excitation potential :

Energy required to excite electron from ground state to any excited state.
Ground state  Excited state

Ist excitation potential = E2  E1  3.4  13.6  10.2 eV.

IInd excitation potential = E3  E1  1.5  13.6  12.1 eV .

(iv) Ionisation energy :

The minimum energy required to relieve the electron from the binding of nucleus.
2
Z eff.
Eionisation  E  En  13.6 eV .
n2

E ionisation
(v) Ionisation potential : Vionisation 
e
(vi) Separation energy :
Energy required to excite an electron from excited state to infinity.
S.E. = E  Eexcited .
(vii) Binding energy :
Energy released in bringing the electron from infinite to any orbit is called its binding energy (B.E.).

13.6
Note :  Principal Quantum Number 'n' = .
(B.E.)
Structure of Atom

(8) Spectral evidence for quantisation :

(Explanation for hydrogen spectrum on the basis of bohr atomic model)

(i) The light absorbed or emitted as a result of an electron changing orbits produces characteristic
absorption or emission spectra which can be recorded on the photographic plates as a series of lines,
the optical spectrum of hydrogen consists of several series of lines called Lyman, Balmar, Paschen,
Brackett, Pfund and Humphrey. These spectral series were named by the name of scientist who
discovered them.

(ii) To evaluate wavelength of various H-lines Ritz introduced the following expression,

1  1 1
    R 2  2 
 c  n1 n2 
2 2 me 4
where, R is =  Rydberg's constant
ch 3
It's theoritical value = 109,737 cm–1 and It's experimental value = 109,677.581cm1

This remarkable agreement between the theoretical and experimental value was great achievment of
the Bohr mode

(iii) Although H- atom consists only one electron yet it's spectra consist of many spectral lines

n=8
n=7
n=6 Humphrey
n=5 series
Pfund
series
n=4
Bracket
Energy level

t
n=3 series
Paschen
series
n=2
Balmer
series

n=1
Lyman
series
 Structure of Atom

(iv) Comparative study of important spectral series of Hydrogen

S.No. Spectral Lies in the Transition n12n22 n12  max n2

max   min   2 2 2
series region n2  n1 (n22 n12 )R R  min n2  n1

(1) Lymen series Ultraviolet n1  1 n1  1 and n2  2 n1  1 and n2  

region 4
n2  2,3,4....  4 1
 max   min  3
3R R

(2) Balmer series Visible n1  2 n1  2 and n2  3 n1  2 and n2  

region
n2  3,4,5....  36 4 9
 max   min 
5R R 5

(3) Paschen Infra red n1 = 3 n1  3 and n2  4 n1  3 and n2  

series region 16
n2  4,5,6....  144 9
 max   min  7
7R R

(4) Brackett Infra red n1  4 n1  4 and n2  5 n1  4 and n2  

series region 25
n2  5,6,7....  16  25 16 9
max   min 
9R R

(5) Pfund series Infra red n1  5 n1  5 and n2  6 n1  5 and n2  

region 36
n2  6,7,8....  25  36 25 11
 max   min 
11R R

(6) Humphrey Far infrared n1  6 n1  6 and n2  7 n1  6 and n2  

series region 49
n2  7,8....  36  49 36 13
 max   min 
13R R

(v) If an electron from nth excited state comes to various energy states, the maximum spectral lines
n(n  1)
obtained will be = . n= principal quantum number.
2
6(6  1) 30
as n=6 than total number of spectral lines =   15.
2 2

(vi) Thus, at least for the hydrogen atom, the Bohr theory accurately describes the origin of atomic spectral lines.

(6) Failure of Bohr Model

(i) Bohr theory was very successful in predicting and accounting the energies of line spectra of hydrogen
i.e. one electron system.
It could not explain the line spectra of atoms containing more than one electron.

(ii) This theory could not explain the presence of multiple spectral lines.
Structure of Atom

(iii) This theory could not explain the splitting of spectral lines in magnetic field (Zeeman effect) and in
electric field (Stark effect). The intensity of these spectral lines was also not explained by the Bohr
atomic model.

(iv) This theory was unable to explain of dual nature of matter as explained on the basis of De broglies
concept.

(v) This theory could not explain uncertainty principle.

(vi) No conclusion was given for the concept of quantisation of energy.

Examples based on Bohr’s atomic model and Hydrogen spectrum

Example: 18 If the radius of 2nd Bohr orbit of hydrogen atom is r2. The radius of third Bohr orbit will be
4 9
(a) r2 (b) 4r2 (c) r3 (d) 9r2
9 4
n2h2 r2 22 9
Solution : (c) r   2  r3  r2
4 2mZe 2 r3 3 4

Example: 19 Number of waves made by a Bohr electron in one complete revolution in 3 rd orbit is
(a) 2 (b) 3 (c) 4 (d) 1
Solution : (b) Circumference of 3 orbit = 2r3
rd

According to Bohr angular momentum of electron in 3rd orbit is

h h 2r3
mvr3 = 3 or 
2 mv 3
h
by De-Broglie equation,  
mv
2r3
  2r3  3
3
i.e. circumference of 3rd orbit is three times the wavelength of electron or number of waves made by Bohr
electron in one complete revolution in 3rd orbit is three.

R11
Example: 20 The degeneracy of the level of hydrogen atom that has energy  is
16
(a) 16 (b) 4 (c) 2 (d) 1
RH RH R 1 2 3
Solution : (a) En      H n=4
n2 n 2
16
i.e. for 4 th sub-shell
1=0

m=0 +1 0 +2 –1 0 +1 +2 –3 –2 –1 0 +1 +2 +3
+1
one s three p five d seven f

i.e. 1+3+5+7=16,  degeneracy is 16

 Structure of Atom

Example: 21 The velocity of electron in the ground state hydrogen atom is 2.18  10 8 ms 1 . Its velocity in the second orbit
would be
(a) 1.09  10 8 ms 1 (b) 4.38  10 8 ms 1 (c) 5.5  10 5 ms 1 (d) 8.76  10 8 ms 1
Solution : (a) We know that velocity of electron in nth Bohr's orbit is given by
Z
v  2.18  10 6 m/ s
n
for H, Z  1
2.18  10 6
 v1  m/ s
1
2.18  10 6
 v2  m / s  1.09  10 6 m / s
2
Example: 22 The ionization energy of the ground state hydrogen atom is 2.18  10 18 J. The energy of an electron in its
second orbit would be
(a)  1.09  10 18 J (b)  2.18  10 18 J (c)  4.36  10 18 J (d)  5.45  10 19 J
Solution : (d) Energy of electron in first Bohr's orbit of H-atom
 2.18  10 18
E J ( ionization energy of H = 2.18  10 18 J )
n2
 2.18  10 18
E2  2
J  5.45  10 19 J
2

Example: 23 The wave number of first line of Balmer series of hydrogen atom is 15200 cm 1 . What is the wave number of
first line of Balmer series of Li 3 ion.
(a) 15200 cm 1 (b) 6080 cm 1 (c) 76000 cm 1 (d) 1,36800 cm 1

Solution : (d) For Li 3 v  v for H  z 2 =15200 ×9= 1,36800 cm 1

Example: 24 The Bohr orbit radius for the hydrogen atom (n = 1) is approximately 0.530Å. The radius for the first excited
state (n = 2) orbit is (in Å)
(a) 0.13 (b) 1.06 (c) 4.77 (d) 2.12
Solution : (d) The Bohr radius for hydrogen atom (n = 1) = 0.530Å
n2 (2)2
The radius of first excited state (n = 2) will be = 0.530   0.530   2.120 Å
Z 1

Example: 25 How many chlorine atoms can you ionize in the process Cl  Cl   e  , by the energy liberated from the
following process :
Cl  e   Cl  for 6  10 23 atoms
Given electron affinity of Cl  3.61eV , and IP of Cl  17.422 eV
(a) 1.24  10 23 atoms (b) 9.82  10 20 atoms (c) 2.02  10 15 atoms (d) None of these
23  23
Solution : (a) Energy released in conversion of 6  10 atoms of Cl ions = 6  10 × electron affinity
23 24
= 6× 10  3.61  2.166  10 eV.
Let x Cl atoms are converted to Cl  ion
Structure of Atom

Energy absorbed  x  ionization energy

x  17.422  2.166  10 24 ; x  1.243  10 23 atoms

Example: 26 The binding energy of an electron in the ground state of the He atom is equal to 24eV. The energy required to
remove both the electrons from the atom will be
(a) 59eV (b) 81eV (c) 79eV (d) None of these
Z2 22
Solution : (c) Ionization energy of He  2
 13.6  2  13 .6  54.4eV
n 1
Energy required to remove both the electrons
 binding energy + ionization energy
 24.6  54.4  79eV

Example: 27 The wave number of the shortest wavelength transition in Balmer series of atomic hydrogen will be
(a) 4215 Å (b) 1437Å (c) 3942Å (d) 3647Å
1  1 1   1 1 
Solution : (d)  RZ 2  2  2   109678  12   2  2 
 shortest  n1 n2  2  

  3.647  10 5 cm  3647 Å

Example: 28 If the speed of electron in the Bohr's first orbit of hydrogen atom is x, the speed of the electron in the third
Bohr's orbit is
(a) x/9 (b) x/3 (c) 3x (d) 9x
Solution : (b) According to Bohr's model for hydrogen and hydrogen like atoms the velocity of an electron in an atom is
2Ze 2 1
quantised and is given by v  so v  in this cass n  3
nh n

Example: 29 Of the following transitions in hydrogen atom, the one which gives an absorption line of lowest frequency is
(a) n=1 to n=2 (b) n  3 to n  8 (c) n  2 to n  1 (d) n  8 to n  3
Solution : (b) Absorption line in the spectra arise when energy is absorbed i.e., electron shifts from lower to higher orbit, out
of a & b, b will have the lowest frequency as this falls in the Paschen series.

Example: 30 The frequency of the line in the emission spectrum of hydrogen when the atoms of the gas contain electrons in
the third energy level are
(a) 1.268  10 14 Hz and 2.864  10 16 Hz (b) 3.214  10 10 Hz and 1.124  10 12 Hz
(c) 1.806  10 12 Hz and 6.204  10 15 Hz (d) 4.568  10 14 Hz and 2.924  10 15 Hz
Solution : (d) If an electron is in 3rd orbit, two spectral lines are possible
(a) When it falls from 3rd orbit to 2nd orbit.
1 1
In equation   3.289  10 15  2  2 
 n1 n2 
1 1 5
 1  3.289  10 15  2
 2   3.289  10 15   4.568  14 14 Hz
 2 3  36
(b) When it falls from 3rd orbit to 1st orbit :
1 1  8
 2  3.289  10 15    2   3.289  10 15   2.924  10 15 Hz
 1 3  9
 Structure of Atom

Example: 31 If the first ionisation energy of hydrogen is 2.179  10 18 J per atom, the second ionisation energy of helium
per atom is
(a) 8.716  10 18 J (b) 5.5250 kJ (c) 7.616  10 18 J (d) 8.016  10 13 J
Z2
Solution : (a) For Bohrs systems : energy of the electron 
n2
Ionisation energy is the difference of energies of an electron (E ), when taken to infinite distance and Er
when present in any Bohr orbit and E is taken as zero so ionisation energy becomes equal to the energy of
electron in any Bohr orbit.
Z2 Z2 E 1
E H  2H ; E He  2He or H  [as Z H  1, Z He  2, nH  1, nHe  1]
nH nHe E He 2  2
or E He  E H  4  2.179  10 18  4  8.716  10 18 Joule per atom.

Example: 32 The ionization energy of hydrogen atom is 13.6eV. What will be the ionization energy of He 
(a) 13.6eV (b) 54.4eV (c) 122.4eV (d) Zero
 2
Solution : (b) I.E. of He  13.6eV  Z
13.6eV  4  54.4eV

Example: 33 The ionization energy of He  is 19.6  10 18 J atom–1. Calculate the energy of the first stationary state of Li 2
(a) 19.6  10 18 J atom-1 (b) 4.41  10 18 J atom–1
(c) 19.6  10 19 J atom-1 (d) 4.41  10 17 J atom1
Solution : (d) I.E. of He   E  2 2 (Z for He  2)
I.E. of Li 2  E  3 3 (Z for Li=3)
I .E.(He  ) 4 9 9
 2
 or I.E. (Li 2 )   I.E.(He  )   19 .6  10 18 = 4.41  10 17 J atom–1
I .E.(Li ) 9 4 4

Bohr – Sommerfeld’s model.

(1) In 1915, Sommerfield introduced a new atomic model to explain the fine spectrum of hydrogen atom.

(2) He gave concept that electron revolve round the nucleus in elliptical orbit.
Circular orbits are formed in special conditions only when major axis and minor axis of orbit are equal.
nh
(3) For circular orbit, the angular momentum = where n= principal quantum number only one
2
component i.e. only angle changes.

(4) For elliptical orbit, angular momentum = vector sum of 2 components. In elliptical orbit two components are,
h
(i) Radial component (along the radius) = nr
2
Where, n r = radial quantum number
h
(ii) Azimuthal component = n  rr
2 r 2 r rr 2 11
1
Where, n  = azimuthal quantum number

 = change  = change
r = change r = constant
Structure of Atom

h h
So angular momentum of elliptical orbit = nr  n
2 2
h
Angular momentum = (nr  n )
2

(5) Shape of elliptical orbit depends on,

Length of major axis n nr  n
 
Length of minor axis n n

(6) n  can take all integral values from l to ‘n’ values of n r depend on the value of n  .
For n = 3, n  can have values 1,2,3 and n r
can have (n –1) to zero i.e. 2,1 and zero respectively. K= 3
K= 2
K= 1
Thus for n = 3, we have 3 paths
 Nuclear
n n nr Nature of path
3 1 3 elliptical
2 1 elliptical
3 0 circular

The possible orbits for n = 3 are shown in figure.

Thus Sommerfield showed that Bohr’s each major level was composed of several sub-levels.
therefore it provides the basis for existence of subshells in Bohr's shells (orbits).

(7) Limitation of Bohr sommerfield model :

(i) This model could not account for,
why electrons does not absorb or emit energy when they are moving in stationary orbits.

(ii) When electron jumps from inner orbit to outer orbit or vice –versa, then electron run entire distance
but absorption or emission of energy is discontinuous.

nh
(iii) It could not explain the attainment of expression of for angular momentum.
2
This model could not explain Zeeman effect and Stark effect.
 Structure of Atom

Dual nature of electron.

(1) In 1924, the french physicist, Louis de Broglie suggested that
if light has both particle and wave like nature, the similar duality must be true for matter.
Thus an electron, behaves both as a material particle and as a wave.

(2) This presented a new wave mechanical theory of matter.

According to this theory, small particles like electrons when in motion possess wave properties.

(3) According to de-broglie,

the wavelength associated with a particle of mass m, moving with velocity v is given by the relation
h
 , where h = Planck’s constant.
mv

(4) This can be derived as follows according to Planck’s equation,

h.c  c
E  h     
   
energy of photon (on the basis of Einstein’s mass energy relationship), E  mc 2
hc h
equating both  mc 2 or  
 mc
which is same as de-Broglie relation.  mc  p

(5) This was experimentally verified by Davisson and Germer by observing diffraction effects with an
electron beam.

Let the electron is accelerated with a potential of V than the Kinetic energy is
1
mv 2  eV ;
2
m 2 v 2  2eVm
mv  2eVm  P ;
h

2eVm

(6) If Bohr’s theory is associated with de-Broglie’s equation then wave length of an electron can be
determined in bohr’s orbit and relate it with circumference and multiply with a whole number
2r
2r  n or  
n
h
From de-Broglie equation,   .
mv
h 2r nh
Thus  or mvr 
mv n 2

Note :  For a proton, electron and an  -particle moving with the same velocity have de-broglie wavelength
in the following order :
Electron > Proton >  - particle.
Structure of Atom

(7) The de-Broglie equation is applicable to all material objects

but it has significance only in case of microscopic particles.
Since, we come across macroscopic objects in our everyday life, de-broglie relationship has no significance
in everyday life.

Examples based on de-Broglie’s equation

Example: 34 An electron is moving with a kinetic energy of 4.55 × 10 25 J. What will be de-Broglie wavelength for this
electron
(a) 5.28 × 10 7 m (b) 7.28 × 10 7 m (c) 2 × 10 10 m (d) 3 × 10 5 m
1
Solution : (b) KE  mv 2  4.55  10  25 J
2
2  4.55  10 25
v2   1 10 6 ; v  10 3 m / s
9.1  10 31
h 6.626  10 34
De-Broglie wavelength     7.28  10 7 m
mv 9.1  10  31  10 3

Example: 35 The speed of the proton is one hundredth of the speed of light in vacuum. What is the de Broglie wavelength?
Assume that one mole of protons has a mass equal to one gram, h  6.626 10 27 erg sec

(a) 3.31 × 10 3 Å (b) 1.33 × 10 3 Å (c) 3.13 × 10 2 Å (d) 1.31 × 10 2 Å

1
Solution : (b) m g
6.023  10 23

h 6.626  10 27
   6.023  10 23 = 1.33  10 11 cm
mv 1  3  10 8 cm sec 1

Heisenberg’s uncertainty principle.

(1) One of the important consequences of the dual nature of an electron is the uncertainty principle,
developed by Warner Heisenberg.

(2) According to uncertainty principle

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

h
Mathematically it is represented as , x . p 
4
 Structure of Atom

Where x  uncertainty is position of the particle, p  uncertainty in the momentum of the particle
Now since p  m v
h
So equation becomes, x. mv 
4
h
or x  v 
4m
The sign  means that the product of x and p (or of x and v ) can be greater than,
h
or equal to but never smaller than . If x is made small, p increases and vice versa.
4
(3) In terms of uncertainty in energy, E and uncertainty in time t, this principle is written as,
h
E . t 
4

h
x . p 
4
Examples based on uncertainty principle

Example: 36 What is the maximum precision with which the momentum of an electron can be known if the uncertainty in
the position of electron is  0.001 Å ? Will there be any problem in describing the momentum if it has a value
h
of , where a 0 is Bohr’s radius of first orbit, i.e., 0.529Å?
2a 0

h
Solution : x . p 
4

 x  0.001 Å  10 13 m
6.625  10 34
 p   5.27  10  22
4  3.14  10 13

Example: 37 Calculate the uncertainty in velocity of an electron if the uncertainty in its position is of the order of a 1Å.
Solution : According to Heisenberg’s uncertainty principle
h
v . x 
4m
h 6.625  10 34
v    5.8  10 5 m sec 1
4m.x 22  31 10
4  9.108  10  10
7

Example: 38 A dust particle having mass equal to 10 11 g, diameter of 10 4 cm and velocity 10 4 cm sec 1 . The error in
measurement of velocity is 0.1%. Calculate uncertainty in its positions. Comment on the result .
Structure of Atom

0.1  10 4
Solution : v   1  10 7 cm sec 1
100
h
 v . x 
4m
6.625  10 27
 x   5.27  10 10 cm
4  3.14  10 11  1  10 7
The uncertainty in position as compared to particle size.
x 5.27  10 10
  4
 5.27  10 6 cm
diameter 10
The factor being small and almost being negligible for microscope particles.

Schrödinger wave equation.

(1) Schrodinger wave equation is given by Erwin Schrödinger in 1926 and based on dual nature of
electron.
(2) In it electron is described as a three dimensional wave in the electric field of a positively charged nucleus.
(3) The probability of finding an electron at any point around the nucleus can be determined by the help of
Schrodinger wave equation which is,

 2   2   2  8 2m
 2  2  (E  V )   0
x 2 y z h2

Where x, y and z are the 3 space co-ordinates,

m = mass of electron, h = Planck’s constant,
E = Total energy, V = potential energy of electron,
 = amplitude of wave also called as wave function.
 = stands for an infinitesimal change.

(4) The Schrodinger wave equation can also be written as :

8 2m
2   (E  V )   0
h2
Where  = laplacian operator.

(5) Physical Significance of  and  2

(i) The wave function  represents the amplitude of the electron wave.
The amplitude  is thus a function of space co-ordinates and time
i.e.   (x, y, z......times)
 Structure of Atom

(ii) For a single particle, the square of the wave function ( 2 ) at any point is proportional to the
probability of finding the particle at that point.

(iii) If  2 is maximum than probability of finding e  is maximum around nucleus.

And the place where probability of finding e  is maximum is called electron density, electron cloud or
an atomic orbital. It is different from the Bohr’s orbit.

(iv) The solution of this equation provides a set of number called quantum numbers
which describe specific or definite energy state of the electron in atom and
information about the shapes and orientations of the most probable distribution of electrons around
the nucleus.

Quantum numbers and Shapes of orbitals.

Quantum numbers
(1) Each orbital in an atom is specified by a set of three quantum numbers (n, l, m) and each electron is
designated by a set of four quantum numbers (n, l, m and s).

(2) Principle quantum number (n)

(i) It was proposed by Bohr’s and denoted by ‘n’.
(ii) It determines the average distance between electron and nucleus, means it is denoted the size of atom.
n2
r  0.529 Å
Z
(iii) It determine the energy of the electron in an orbit where electron is present.
Z2
E  313.3 Kcal per mole
n2
(iv) The maximum number of an electron in an orbit represented by this quantum number as 2n 2 .
No energy shell in atoms of known elements possess more than 32 electrons.

(v) It gives the information of orbit K, L, M, N------------.

(vi) The value of energy increases with the increasing value of n.
(vii) It represents the major energy shell or orbit to which the electron belongs.

(viii) Angular momentum can also be calculated using principle quantum number
nh
mvr 
2
Structure of Atom

(3) Azimuthal quantum number (l)

(i) Azimuthal quantum number is also known as angular quantum number.
Proposed by Sommerfield and denoted by ‘l’.

(ii) It determines the number of sub shells or sublevels to which the electron belongs.

(iii) It tells about the shape of subshells.

(iv) It also expresses the energies of subshells s  p  d  f (increasing energy).

(v) The value of l  (n  1) always where ‘n’ is the number of principle shell.

(vi) Value of l = 0 1 2 3………..(n-1)

Name of subshell = s p d f
Shape of subshell = Spherical Dumbbell Double dumbbell Complex

h
(vii) It represent the orbital angular momentum. Which is equal to l(l  1)
2
(viii) The maximum number of electrons in subshell  2(2l  1)
s  subshell  2 electrons d  subshell  10 electrons
p  subshell  6 electrons f  subshell  14 electrons.

(ix) For a given value of ‘n’ the total value of ‘l’ is always equal to the value of ‘n’.

(x) The energy of any electron is depend on the value of n & l because total energy = (n + l).
The electron enters in that sub orbit whose (n + l) value or the value of energy is less.

(4) Magnetic quantum number (m)

(i) It was proposed by Zeeman and denoted by ‘m’.

(ii) It gives the number of permitted orientation of subshells.

(iii) The value of m varies from –l to +l through zero.

(iv) It tells about the splitting of spectral lines in the magnetic field
 Structure of Atom

i.e. this quantum number proved the Zeeman effect.

(v) For a given value of ‘n’ the total value of ’m’ is equal to n 2 .

(vi) For a given value of ‘l’ the total value of ‘m’ is equal to (2l  1).

(vii) Degenerate orbitals : Orbitals having the same energy are known as degenerate orbitals. e.g. for p
subshell p x p y p z

(viii) The number of degenerate orbitals of s subshell =0.

(4) Spin quantum numbers (s)

(i) It was proposed by Goldshmidt & Ulen Back and denoted by the symbol of ‘s’.

(ii) The value of ' s' is  1/2 and - 1/2, which is signifies the spin or rotation or
direction of electron on it’s axis during movement.

(iii) The spin may be clockwise or anticlockwise.

h
(iv) It represents the value of spin angular momentum is equal to s(s  1).
2
(v) Maximum spin of an atom  1 / 2  number of unpaired electron.

Magnetic field

N S

+1/2 –1/2

S N

(vi) This quantum number is not the result of solution of schrodinger equation as solved for H-atom.
Structure of Atom

Distribution of electrons among the quantum levels

Designation of Electrons Total no. of
n l m s
orbitals present electrons
1 (K shell) 0 0 +1/2, –1/2 1s 2 2
2 (L shell) 0 0 1 / 2,  1 / 2 2s 2
+1  1 / 2,  1 / 2  8

1 0  1 / 2,  1 / 2 2p 6 
 1 / 2,  1 / 2
–1

3 (M shell) 0 0 1 / 2,1 / 2 3s 2 
+1  1 / 2,1 / 2 

1 0  1 / 2,1 / 2 3p 6 

–1 1 / 2,1 / 2 

 18

 1 / 2,1 / 2 

+2  1 / 2,1 / 2 
+1  1 / 2,1 / 2 3d 
 
2 0  1 / 2,1 / 2 
 1 / 2,1 / 2 
–1 10 
–2
0 0 1 / 2,1 / 2 4s
2 
+1  1 / 2,1 / 2 

1 0  1 / 2,1 / 2 4p 6 
 1 / 2,1 / 2 
–1 




+2  1 / 2,1 / 2 

+1  1 / 2,1 / 2 
 1 / 2,1 / 2 
2 0 4d 10  32

–1  1 / 2,1 / 2 

 1 / 2,1 / 2 
–2

4(N shell) 

+3 

+2 
+1 
4f 14 
3 +0
–1
 Structure of Atom

–2  1 / 2,1 / 2
–3  1 / 2,1 / 2
 1 / 2,1 / 2

 1 / 2,1 / 2
 1 / 2,1 / 2

 1 / 2,1 / 2
 1 / 2,1 / 2

Shape of orbitals

(1) Shape of ‘s’ orbital

(i) For ‘s’ orbital l=0 & m=0 so ‘s’ orbital have only one unidirectional Z
orientation i.e. the probability of finding the electrons is same in all Y
directions.

X
(ii) The size and energy of ‘s’ orbital with increasing ‘n’ will be
1s  2s  3s  4 s. Nucleus

(iii) It does not possess any directional property. s orbital has spherical shape.

(2) Shape of ‘p’ orbitals

(i) For ‘p’ orbital l=1, & m=+1,0,–1 means there are three ‘p’ orbitals, which is symbolised as
p x , py , pz .

(ii) Shape of ‘p’ orbital is dumb bell in which the two lobes on opposite side separated by the nodal plane.

(iii) p-orbital has directional properties.

Z Z
Y Z
Y Y
Nodal Nodal
Plane Plane Nodal
X Nodal X Plane X
Plane
Px orbital Py orbital Nodal Pz orbital
Plane
Structure of Atom

(2) Shape of ‘d’ orbital

(i) For the ‘d’ orbital l =2 then the values of ‘m’ are –2,–1,0,+1,+2.
It shows that the ‘d’ orbitals has five orbitals as d xy , d yz , d zx , d x 2 y 2 , d z 2 .

(ii) Each ‘d’ orbital identical in shape, size and energy.

(iii) The shape of d orbital is double dumb bell .
(iv) It has directional properties.

Z Z Z Y Y
Y Y Y
Z

X X X X X

dZX dXY dYZ dX2–Y2 dZ2

(4) Shape of ‘f’ orbital

(i) For the ‘f’ orbital l=3 then the values of ‘m’ are –3, –2, –1,0,+1,+2,+3.
It shows that the ‘f’ orbitals have seven orientation as
fx( x 2  y 2 ), fy( x 2  y 2 ), fz( x 2  y 2 ), fxyz , fz 3 , fyz 3 and fxz 2 .

(ii) The ‘f’ orbital is complicated in shape.

Electronic configuration principles.

The distribution of electrons in different orbitals of atom is known as electronic configuration of the atoms.
Filling up of orbitals in the ground state of atom is governed by the following rules:

(1) Aufbau principle

(i) Auf bau is a German word, meaning ‘building up’.
(ii) According to this principle,
“In the ground state, the atomic orbitals are filled in order of increasing energies
i.e. in the ground state the electrons first occupy the lowest energy orbitals available”.
(iii) In fact the energy of an orbital is determined by the quantum number n and l with the help of (n+l)
rule or Bohr Bury rule.
 Structure of Atom

(iv) According to this rule

(a) Lower the value of n + l, lower is the energy of the orbital and such an orbital will be filled up first.
(b) When two orbitals have same value of (n+l) the orbital having lower value of “n” has lower energy
and such an orbital will be filled up first .
Thus, order of filling up of orbitals is as follows:

1s  2s  2p  3s  3 p  4 s  4 p  5s  4d  5 p  6s  6 f  5d

(2) Pauli’s exclusion principle

(i) According to this principle,
“No two electrons in an atom can have same set of all the four quantum numbers n, l, m and s .
(ii) In an atom any two electrons may have three quantum numbers identical
but fourth quantum number must be different.
(iii) Since this principle excludes certain possible combinations of quantum numbers
for any two electrons in an atom, it was given the name exclusion principle.
Its results are as follows :

(a) The maximum capacity of a main energy shell is equal to 2n 2 electron.

(b) The maximum capacity of a subshell is equal to 2(2l+1) electron.
(c) Number of sub-shells in a main energy shell is equal to the value of n.

(d) Number of orbitals in a main energy shell is equal to n 2 .

(e) One orbital cannot have more than two electrons.
(iv) According to this principle
An orbital can accommodate at the most two electrons with spins opposite to each other.
It means that an orbital can have 0, 1, or 2 electron.
(v) If an orbital has two electrons they must be of opposite spin.

Correct Incorrect

(3) Hund’s Rule of maximum multiplicity

(i) This rule provides the basis for filling up of degenerate orbitals of the same sub-shell.

(ii) According to this rule “Electron filling will not take place in orbitals of same energy until all the
available orbitals of a given subshell contain one electron each with parallel spin”.
 Structure of Atom

(iii) This implies that electron pairing begins with fourth, sixth and eighth electron in p, d and f orbitals of
the same subshell respectively.

(iv) The reason behind this rule is related to repulsion between identical charged electron present in the
same orbital.

(v) They can minimize the repulsive force between them serves by occupying different orbitals.

(vi) Moreover, according to this principle,

The electron entering the different orbitals of subshell have parallel spins.

This keep them farther apart and lowers the energy through electron exchange or resonance.

(vii) The term maximum multiplicity means that

The total spin of unpaired e  is maximum in case of correct filling of orbitals as per this rule.

Energy level diagram

The representation of relative energy levels of various atomic orbital is made in the terms of energy level

diagrams.

One electron system : In this system 1s 2 level and all orbital of same principal quantum number have

same energy, which is independent of (l). In this system l only determines the shape of the orbital.

Multiple electron system : The energy levels of such system not only depend upon the nuclear charge

but also upon the another electron present in them.

5
4s 4p 4d 4f 6p
5d
4 4f
6s
5p

3s 3p 3d 4d
5s
4p
Energy

3 3d
4s
2s 2p 3p

2 3s
2p

2s
1s
Energy

1s

Energy level diagram of one Energy level diagram of multiple

electron system electron system
 Structure of Atom

Diagram of multi-electron atoms reveals the following points :

(i) As the distance of the shell increases from the nucleus, the energy level increases.
For example energy level of 2 > 1.

(ii) The different sub shells have different energy levels which possess definite energy.
For a definite shell, the subshell having higher value of l possesses higher energy level.
For example in 4th shell.
Energy level order 4f > 4d > 4p > 4s
l= 3 l=2 l=1 l= 0

(iii) The relative energy of sub shells of different energy shell can be explained in the terms of the (n+l) rule.
(a) The sub-shell with lower values of (n + l) possess lower energy.
For 3d n=3 l= 2  n+l=5
For 4s n=4 l=0 n+l=4
(b) If the value of (n + l) for two orbitals is same, one with lower values of ‘n’ possess lower energy level.

Extra stability of half filled and completely filled orbitals:

Half-filled and completely filled sub-shell have extra stability due to the following reasons :

(i) Symmetry of orbitals

(a) It is a well kown fact that symmetry leads to stability.

(b) Thus, if the shift of an electron from one orbital to another orbital differing slightly in energy results in
the symmetrical electronic configuration. It becomes more stable.

(c) For example p 3 , d 5 , f 7 configurations are more stable than their near ones.

(ii) Exchange energy

(a) The electron in various subshells can exchange their positions, since electron in the same subshell have
equal energies.

(b) The energy is released during the exchange process with in the same subshell.

(c) In case of half filled and completely filled orbitals, the exchange energy is maximum and is greater than
the loss of orbital energy due to the transfer of electron from a higher to a lower sublevel
e.g. from 4s to 3d orbitals in case of Cu and Cr .
Structure of Atom

(d) The greater the number of possible exchanges between the electrons of parallel spins present in the
degenerate orbitals, the higher would be the amount of energy released and more will be the stability.

(e) Let us count the number of exchange that are possible in d 4 and d 5 configuration among electrons
with parallel spins.

d4 (1) (2) (3)

–
3 exchanges by 1st e 2 exchanges by 2nd e–
Only 1 exchange by 3rd e–

To number of possible exchanges = 3 + 2 + 1 =6

d5 (1) (2) (3)

4 exchanges by 1st e– 3 exchanges by 2nd e–
2 exchange by 3rd e–

(4)

1 exchange by 4th e–

To number of possible exchanges = 4 + 3 + 2 +1 = 10

 Structure of Atom

Electronic configurations of Elements.

(1) On the basis of the elecronic configuration priciples the electronic configuration of various elements are
given in the following table :
Electronic Configuration (E.C.) of Elements Z=1 to 36
Atomic
Element 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
Number
H 1 1
He 2 2
Li 3 2 1
Be 4 2 2
B 5 2 2 1
C 6 2 2 2
N 7 2 2 3
O 8 2 2 4
F 9 2 2 5
Ne 10 2 2 6
Na 11 2 2 6 1
Mg 12 2
Al 13 2 1
Si 14 10 2 2
P 15 electrons 2 3
S 16 2 4
Cl 17 2 5
Ar 18 2 2 6 2 6
K 19 2 2 6 2 6 1
Ca 20 2
Sc 21 1 2
Ti 22 2 2
V 23 3 2
Cr 24 5 1
Mn 25 5 2
Fe 26 6 2
Co 27 18 7 2
Ni 28 electrons 8 2
Cu 29 10 1
Zn 30 10 2
Ga 31 10 2 1
Ge 32 10 2 2
As 33 10 2 3
Se 34 10 2 4
Br 35 10 2 5
Kr 36 2 2 6 2 6 10 2 6
Structure of Atom

(3) The above method of writing the electronic configurations is quite cumbersome.
Hence, usually the electronic configuration of the atom of any element is simply represented
by the notation.

NUMBER OF
ELECTRONS

x
PRESENT

nl
NUMBER OF SYMBOL OF
PRINCIPAL SUBSHELL
SHELL

e.g. 1s2 means 2 electrons are present in the s- subshell of

the 1st main shell.

(3) (i) Elements with atomic number 24(Cr), 42(Mo) and 74(W) have ns 1 (n  1) d 5 configuration
and not ns 2 (n  1) d 4 due to extra stability of these atoms.

(iii) Elements with atomic number 29(Cu), 47(Ag) and 79(Au) have ns 1 (n  1) d 10 configuration
instead of ns 2 (n  1) d 9 due to extra stability of these atoms.

Cr (24) [Ar] 3d5 Cu (29) [Ar] 3d10

4s1 4s1

(4) In the formation of ion, electrons of the outer most orbit are lost.
Hence, whenever you are required to write electronic configuration of the ion,
first write electronic configuration of its atom and take electron from outermost orbit.
If we write electronic configuration of Fe 2 (Z  26, 24 e  ),
it will not be similar to Cr (with 24 e  ) but quite different.
Fe Ar  4 s 2 3d 6 

6 
outer most orbit is 4th shell
Fe Ar  4 s 3d 
2 

hence, electrons from 4s have been removed to make Fe 2 .

(5) Ion/atom will be paramagnetic if there are unpaired electrons.

Magnetic moment (spin only) is   n(n  2) BM (Bohr Magneton).
(1BM  9.27  10 24 J / T) where n is the number of unpaired electrons.
 Structure of Atom

(5) Ion with unpaired electron in d or f orbital will be coloured.

Thus, Cu  with electronic configuration Ar  3d 10 is colourless
and Cu 2 with electronic configuration Ar  3d 9 (one unpaired electron in 3d) is coloured (blue).

(6) Position of the element in periodic table on the basis of electronic configuration can be determined as,

(i) If last electron enters into s-subshell, p-subshell, penultimate d-subshell and anti penultimate f-subshell
then the element belongs to s, p, d and f – block respectively.

(ii) Principle quantum number (n) of outermost shell gives the number of period of the element.

(iii) If the last shell contains 1 or 2 electrons (i.e. for s-block elements having the configuration ns 1 2 ),
the group number is 1 in the first case and 2 in the second case.

(iv) If the last shell contains 3 or more than 3 electrons

(i.e. for p-block elements having the configuration ns 2 np16 ),
the group number is the total number of electrons in the last shell plus 10.

(v) If the electrons are present in the (n –1)d orbital in addition to those in the ns orbital
(i.e. for d-block elements having the configuration (n –1) d 110 ns 12 ),
the group number is equal to the total number of electrons present in the (n –1)d orbital
and ns orbital.

NOTE :

 All lines in the visible region are of Balmer series but reverse is not true i.e., all Balmer lines will not fall in visible region.

 A part of an atom up to penultimate shell is a kernel or atomic core

 If the energy supplied to hydrogen atom is less than 13.6 eV it will awpt or absorb only those quanta which can take it
to a certain higher energy level i.e., all those photons having energy less than or more than a particular energy level will not
be absorbed by hydrogen atom, but if energy supplied to hydrogen atom is more than 13.6eV then all photons are
absorbed and excess energy appear as kinetic energy of emitted photo electron.

 No of nodes in any orbital  (n  l  1)

 No of nodal planes in an orbitals  l

 The d orbital which does not have four lobes is dz 2

 The d orbital whose lobes lie along the axis is d x 2 y 2

Structure of Atom

h
 Spin angular momentum  s(s  1)
2
n
 Total spin   ; where n is no of unpaired e 
2

 Magnetic moment  n(n  2) B.M. (Bohr magnetron)

of n unpaired e 

 Ion with unpaired electron in d or f orbital will be coloured.

 Exception of E.C. are Cr (24) , Cu(29) , Mo(42) , Ag(47) ,

W(74) , Au(79) .
2r h
 No. of waves n  (where   )
 mv
v
 No. of revolutions of e  per second is  .
2r
 The solution of schrodinger wave equation gives principal, azimuthal and magnetic quantum numbers but not the spin
quantum number.

 In the Rydberg formula, when n2   the line produced is called the limiting line of that series.
 Among various forms of visible light, violet colour has shortest wavelength, highest frequency and highest energy.
 Red coloured light has largest wavelength, least frequency and lowest energy in visible light.
 Elements give line spectra. The line spectrum is characteristic of the excited atom producing it. No two elements have
identical line spectrum.
 The line spectrum results from the emission of radiations from the atoms of the elements and is therefore called as
atomic spectrum.
 Atoms give line spectra (known as atomic spectrum) and the molecules give band spectra (known as molecular spectrum).
 The negative potential at which the photoelectric current becomes zero is called cut off potential or stopping potential.

 When energy or frequency of scattered ray is lesser than the incident ray, it is known as Compton effect.

 The instrument used to record solar spectrum is called spectrometer or spectrograph developed by Bunsen and Kirchoff
in 1859.

 The intensities of spectral lines decreases with increase in the value of n . For example, the intensity of first Lyman line
(2  1)

is greater than second line (3  1) and so on.

 In Balmer series of hydrogen spectrum the first line (3  2) is also known as L line. The second line (4  2) is L
line.
The line from infinity energy shell is called limiting line.
Structure of Atom