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1ST YEAR CHEMISTRY NOTES

CHAPTER 2: ATOMIC STRUCTURE

Properties of Cathode Rays

1. Effect of Electric Field

 Cathode rays deflect towards +ve plate (anode) in electric field

 Studied by J.J Thomson in 1897

2. Charge

 Deflect to +ve plate in electric field shows that cathode rays –ve charge.

3. Effect of Magnetic Field

 They deflect in magnetic field

 Proved by J.Perrin in 1895

4. Fluorescence

 They produce greenish fluorescence on strike walls of glass tube

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5. Shadow Formation

 Cathode rays cast a sharp shadow when an opaque object placed in their
path.
 Proved by Hittorf in 1869
 This shows wave-like nature of cathode rays.

6. Path

 Cathode rays travel in straight path as they form sharp shadow of opaque
objects placed in their path
 Proved by Hittorf in 1869

7. Momentum

 They can drive a small paddle wheel placed in their path.

 This shows that they are material particle and have some momentum
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8. Energy

 They possess energy

 They produce heat when they fall on platinum foil and foil begins to glow

9. Penetration

 They are capable of penetration in metallic sheets like aluminium of gold

10. Ionization

 Cathode rays can ionizes gases

11. Chemical Change

 They can cause chemical change in a material on which they fall

12. X-ray Production

 Cathode rays produce x-rays when they fall on anode of heavy metals (with
large atomic masses)

13. Charge to mass ratio (e/m)

 Charge to mass ratio e/m is 1.7588 × 1011 Ckg–1

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 Determined by J.J.Thomson
 He proved that cathode rays are electrons
 e/m of electrons (cathode rays) does not depend on the type of gas filled in
discharge tube. It is always same. This proves that electrons are present in all
atoms.

MEASUREMENT OF CHARGE TO MASS RATION (E/M) OF ELECTRON

1) Introduction

 J.J Thomoson determined e/m of electron

 In 1897

2) Experiment

 J.J Thomson applied and electric and magnetic field to a beam of electrons
 He determined e/m of electron by comparing the strengths of electric and
magnetic fields

In the absence of fields

 In the beginning J.J Thomson applied neither electric nor magnetic field
 The beam of electrons passed undeflected and struck at point B

b) In the presence of electric field

 Beam of electrons deflected towards +ve plate of electric field

 Beam of electrons struck at point A above the point B

c) In the presence of magnetic field

 Magnetic field was applied perpendicular to the electric field

 Beam of electrons deflected at point C below the point A

d) In the presence of both fields

 At the end J.J Thomson applied both electric and magnetic fields
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 Both fields were adjusted so that beam struck again at point B

3) Calculation of e/m of electron

 e/m was determined by comparing the strength of electric and magnetic

fields
 J.J Thomson determined e/m of electron equal to 1.7588 × 1011 Ckg-1
 t means that 1 kg of electrons has 1.7588 × 1011 coulombs charge

4) Diagram

1) Introduction

 R.A Millikan measured charge on electron in 1909

 Experiment is known as Millikan’s Oil Drop Experiment

2) Construction

Millikan constructed a box which consisted of following parts;

a) Two chambers

 Upper chamber was filled with gas

 Pressure of gas was adjusted by vacuum pump
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b) Electrodes

 Two electrodes A and A1 were installed

 Electrodes were attached with electricity to generate electric field
 Upper electrode had a hole

c) Atomizer

 An apparatus that converts oil into very small droplets

d) X-ray source

 For ionization of gas

e) Arc lamp

 To illuminate space between chambers

f) Microscope

 To observe droplet and to determine velocity of droplet

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2) Working

 A fine spray of oil droplets was created by an atomizer

 Few droplets entered the hole, then hole was closed
 An arc lamp was used to illuminate the space between the electrodes
 One droplet was taken under the focus
 The droplet moved downward under the effect of gravity
 Downward velocity of droplet (V1) was determined;
V1 𝖺 mg eq.1
 Then air between the chambers was ionized
 Oil droplet took up an electron and got charged
 Electrodes A and A1 were connected to battery and electric field E was
applied.
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 The droplet moved upward (to +ve electrode) against the gravity with
velocity V2.
 Upward force of electric field was equal to product of strength of electric
field E and charge on electron e.
Upward force = e E
 Upward velocity V2 𝖺 upward force – downward force
V2 𝖺 e E – mg eq.2
 Dividing eq.1 by eq.2
𝑉1 𝑚g
=
𝑉2 𝑒𝐸−𝑚g

4) Charge on Electron

 V1 and V2 can be determined (distance/time) using microscope, factors E

and g are known, mass of droplet can found by suspending the droplet in
chamber, hence charge on electron e can be determined, which is 1.6022 ×
10–19 coulombs

POSITIVE-RAYS OR CANAL RAYS

(Discovery of Proton by Goldstein, a German Physicist 1886)

1) Introduction

 In a discharge tube, atoms or molecules lose electrons forming positive ions.

 Typical example is of ionization of Neon gas
 Positive ions move towards cathode

2) Construction

 One metre long discharge tube was made

 Discharge tube had perforated cathode
 Electrodes were connected to battery
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3) Working

 When electric current was passed through the gas under reduced pressure,
some rays are produced from cathode which traveled away from cathode.
 Such rays ionize the gas in the middle of the discharge tube.
 They knocked out electron from the gas molecules.
 As a result positive ions were produced, which start moving towards the
perforated cathode

 Since these rays passed through the canals (small holes) of cathode so they
were also called as “Canal rays”.
 Later on they were called Positive rays because they carried positive charge

4) Properties of Positive Rays

i) They travel in straight lines perpendicular to the anode surface

ii) They can be deflected in electric field

iii) Their deflection is towards cathode showing that they are positively charged

iv) They produce flashes on ZnS plate

v) Their e/m ratio is smaller than that of an electron

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vi) Their e/m ratio depends upon the nature of the gas. Highest e/m is obtained if
hydrogen gas present in discharge tube.
vii) The mass of a +ve particle is never less than that of a proton

viii) The positive particle obtained from H2 gas is the lightest among all the positive
particles

ix) A particle obtained from positive rays is called proton, a name suggested by
Rutherford

x) The mass of a proton is 1836 times more than that of an electron

xi) As proton is present in all the atoms therefore proton is a common constituent
of all matter
DISCOVERY OF NEUTRONS

Introduction

 After the discovery of electrons and protons in an atom, nothing extra was
known about it until 1932.
 Rutherford in 1920 predicted that some neutral particles must also be
present in it because he noticed that atomic mass of atoms could not be
explained if it were supposed that atoms had only electrons and protons
 James Chadwick in 1932 performed an experiment and proved that certain
neutral particles also exist in nucleus of an atom
 He was awarded Nobel Prize in Physics in 1935 for this discovery

Experiment by James Chadwick

 A stream of a-particles produced from Polonium (Po) was directed at target

metal foil 4Be9.
 It was noticed that some penetrating radiations were produced.
 These radiations were called neutrons, because the charge detector showed
them to be neutral.
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Properties of neutrons

Neutrons have the following properties,

I. Free neutron decays into a proton with the emission of electron and
neutrino.

II. They cannot ionize gases.

III. They are highly penetrating particles.
IV. When neutrons “travel with energy 1.2 Mev or more, they are called Fast
Neutrons.
V. When have energy below 1 e.v., they are called slow neutrons.
VI. They are not deflected in electric and magnetic fields. Hence they are neutral
in nature.
VII. They can knockout high speed protons from paraffins, water, paper and
cellulose.
VIII. Slow neutrons are more effective than the fast ones for the fission purposes.
IX. When neutrons are used as projectile, they can carry out the nuclear
reactions

X. When slow moving neutrons hit the Cu metal, (radiations are emitted

Because of their intense biological effects, they are used in the treatment of
cancer
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THE DISCOVERY OF NUCLEUS (RUTHERFORD’SEXPERIMENT, 1910-11

1) Experiment

 After the discovery of electron and proton in an atom, the next problem was
to locate their positions
 Rutherford in 1910 performed an experiment by bombarding 𝑎- particles
(2He4) from a radioactive element (Ra or Po) on a thin metallic foil (0.0004 cm
thick)
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2) Rutherford’s Conclusions (Rutherford’s Atomic Model)

a) An atom consists of a small heavy positively charged portion called Nucleus.

b) There is a negatively charged portion which surround the nucleus containing

electrons called extra- nuclear portion or planetary.

c) The number of protons in the nucleus is equal to the no of electrons in the

planetary.

d) The electrons revolve around the nucleus.

e) The centripetal force is equal to the electrostatic force.

f) Only a very small volume is occupied by the

3) Drawbacks in Rutherford’s Atomic Model

 According to the classical electromagnetic theory the revolving electron

arround nucleus should lose energy continuously and ultimately it should fall
in to the nucleus.
 If electron emits energy continuously, it should form continuous spectrum.
But actually line spectrum is obtained

BOHR’S ATOMIC THEORY

a) Introduction

 Neil Bohr (1913), an English scientist, removed these defects and proposed
another possible structure of atom called as the Bohr's atomic model.

b) Postulates

According to this model;

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 Electrons revolve around the nucleus in definite energy levels called orbits or
shells
 As long as an electron remain in a shell it never gains or losses energy
 The gain or loss of energy occurs within orbits only due to jumping of
electrons from one energy level to another energy level

 Angular momentum (mvr) of an electron is equal to nh/2π

 The angular momentum of an orbit depends upon its quantum number and it
is an integral multiple of the factor h/2π
mvr = nh/2 π Where n = 1, 2, 3,

DERIVATION OF RADIUS OF AN ORBIT OF AN ATOM

Derivation of Radius of an Atom

Let us consider

 Charge of electron = e
 Atomic no of atom = Z
 Total charge = Ze
 Mass of electron = m
 Velocity of electron = v
 Radius of electron = r

Revolving electron needs centripetal force. It is provided by electrostatic force of

attraction between nucleus and electron

Centripetal force = Electrostatic force

 𝑚𝑣2
Centripetal force =
𝑟
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 Electrostatic force is given by Coulomb’s law

𝑧𝑒+×𝑒−
=
4𝜋𝗌𝑜𝑟2
𝑧𝑒2
=
4𝜋𝗌𝑜𝑟2

𝑚𝑣2 𝑧𝑒2
=
𝑟 4𝜋𝗌𝑜𝑟2

Where ∈𝑜 is the vacuum permittivity constant with a value 8.84 x 10–12 C2 J–1 m–1
2
𝑚𝑣2 = 𝑧𝑒
4𝜋𝗌𝑜𝑟
𝑧𝑒2
or 𝑟 =
4𝜋𝗌𝑜𝑚𝑣2

𝑧𝑒2 ------------------
𝑟 = × 1 eq.A
4𝜋𝗌𝑜𝑚 𝑣2

Radius of a moving electron is inversely proportional to the square of its velocity

Velocity ‘v’ is determined from angular momentum

𝑛ℎ
mvr = 2𝜋
𝑛ℎ
or v = 2𝜋𝑚𝑟
By taking square on both sides;

2 𝑛2ℎ2
𝑣 =
4𝜋2𝑚2𝑟2
By putting 𝑣2 in equation A;
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𝑧𝑒2 1
𝑟 = × 𝑛2ℎ 2
4𝜋𝗌𝑜𝑚
4𝜋 2𝑚 2r2

𝑧𝑒2 4𝜋2𝑚2𝑟2
𝑟 = ×
4𝜋𝗌𝑜𝑚 𝑛2ℎ2

𝑧𝑒2𝜋𝑚𝑟
1 =
𝗌𝑜𝑛2ℎ2

1 𝑧𝑒2𝜋𝑚𝑟
=
1 𝗌𝑜𝑛2ℎ2

Through cross multiply;

𝑧𝑒2𝜋𝑚𝑟 = s𝑜𝑛2ℎ2
𝗌𝑜𝑛2ℎ2
𝑟 =
𝑧𝑒 2 𝜋𝑚
For Hydrogen Z = 1, therefore;

𝗌𝑜𝑛2ℎ2
𝑟 =
1×𝑒2 𝜋𝑚
𝗌𝑜𝑛2ℎ2
𝑟=
𝜋𝑚𝑒 2
𝗌𝑜 ℎ 2
or 𝑟 = 𝑛2 ×
𝜋𝑚𝑒2
𝗌𝑜 ℎ2
factor = constant = 𝑎𝑜
𝜋𝑚𝑒2

𝑟 = 𝑛2 × 𝑎 𝑜
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Derivation of Energy of electron
What is required for derivation??
Derivation of Potential Energy (P.E)
Potential energy of electron is equal to work done on electron in moving it from infinity to
orbit of electron
P.E = work done
P.E = F.r
𝑍𝑒2
𝐹=
4𝜋 ∈𝑜 𝑟2
Derivation of Energy of electron
Difference of Energy between two orbits
Derivation of Frequency

By comparing two equations

For Hydrogen atom Z = 1
Defects of Bohr’s Atomic Model

• Bohr’s atomic model is applicable to one electron system

1
• Cannot explain the origin of the spectrum of multi-electrons or polyelectronic
systems like He, Li, Be etc.

• When a spectrum of Hydrogen gas is seen through a powerful

2
spectrometer, the origin of spectral lines are replaced by several very fine
lines
• Original lines are divided into other fine lines. Bohr’s theory cannot explain
this fine structure

• Bohr suggested circular orbits of electrons around the nucleus of H-atom.

3 But it is proved that the motion of electron is not in a single plane, but takes
place in three-dimensional space
Defects of Bohr’s Atomic Model
• Bohr’s theory cannot explain the effect of magnetic field (Zeeman Effect) and
4 electric field (Stark Effect) on the spectra of atoms

• Zeeman’s Effect: “The splitting of spectral lines of H-spectrum under the

influence of magnetic field.”

• Stark’s Effect: “The splitting of spectral lines of H-spectrum

under the influence of electric field.”

Stark Effect
 Defects of Bohr’s Atomic Model

• In Bohr’s atom, the electrons are moving in orbits with specific velocities in
5 specific radii.

• But according to Heisenberg’s uncertainty principle, both the exact

position and velocity of electron cannot be measured simultaneously

Solution to Defects of Bohr’s Atomic Model

• Schrodinger gave a wave equation for hydrogen atom

• According to him, although the position and velocity of an electron cannot be found
exactly
• The probability of finding an electron can be ascertained
• The maximum probability is at a distance of 0.0529 nm
 1st Year Chemistry
Federal Board
Chapter 2: Atomic Structure
Topic: Plank’s Quantum Theory

Plank’s Quantum Theory

a) Introduction

 Proposed by Max Plank

 In 1900
 About nature of light

b) Main Postulates

1) Emission of Energy

 Energy is not emitted or absorbed continuously

 It is emitted or absorbed in the form of wave packets or quanta
 In case of light the quantum of energy is often called photon

2) Relation of Energy to Frequency

 The number of waves passing through a point per second is called Frequency
  The amount of energy associated with quantum of radiation is directly
proportional to the frequency (𝑢) of radiation, i.e

 Quantum Nature A body can emit or absorb energy only in terms of integral
multiple of a quantum

3) Relation of Energy to Wavelength

 The distance between two adjacent crests or troughs is called wavelength

 Energy is inversely proportional to wavelength

4) Relation of Energy to wave number

 Number of waves per unit distance is called wave number.

 Energy is directly proportional to wave number

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HYDROGEN SPECTRUM

1) Introduction

 The display of spectral lines of hydrogen is called hydrogen spectrum

 When Hydrogen is enclosed in a container and heated, it emits radiation
 These radiation are actually emitted due to excitation and de-excitation of
electron of hydrogen

2) History

 The first spectral lines were discovered in 1887 by Lyman and Balmer
 Neil Bohr presented his explanation of line spectra in 1913

3) Origin of Hydrogen Spectrum on the Basis of Bohr’s Model

a) Excitation

 According to Bohr when current is passed through the hydrogen gas in the
discharge tube at low pressure, the molecules of hydrogen break in to atoms
 These atoms absorb energy from the electric spark
 The electrons of hydrogen atoms are excited to high energy levels
 The higher energy orbits to which the electron migrates depend upon the
amount of energy absorbed by the electron.
 This gives absorption spectrum

b) De-excitation

 Excited electrons being unstable come back to one of the lower energy levels
 The electrons may come to the lowest energy levels
 They emit energy, they had absorbed
 This gives emission spectrum

4) Spectral Lines

a) Bohr Prediction
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 Bohr predicted the wave number in the hydrogen emission spectrum and the
electron transition using following equation

 The wave number of different spectral lines can be calculated corresponding

to the values of n1 and n2.

b) Spectral Series

 In the hydrogen spectrum, different series of lines have been identified for n1
and n2 values. These series are

 Regions of Spectral Lines

 Only the Balmer series was observed in the visible part of the spectrum.
 Lyman series lie in the ultraviolet region
 Paschen, Brackett and Pfund series have been observed in the infrared
region

i) Lyman Series

 The various lines in Lyman series got their explanation by considering that
the electrons of hydrogen atom fall back to n=1 from higher levels
 Values of wave numbers lie in the UV region of the spectrum.
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 Limiting line shows the difference between first level and infinite level is the
ionization energy of hydrogen atom
 All these lines of Lyman series have close values. They appear in the form of a
group

ii) Balmer series

 In this series the electrons fall back to n=2

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iii) Paschen Series

 The electrons from higher levels fall back to n=3

 These are again the groups of lines to each other and appear in IR region

iv) Brackett series

 The electrons from higher levels fall back to n=4

 These lines lie in IR region

v) Pfund series

 The electrons from higher energy levels fall back to n=5

 These lines lie in IR region
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X- RAYS

Definition

Electromagnetic rays of very short wavelength produced when cathode rays hit a
heavy metal target are called X-rays

Discovery

 Discovered by Wilhelm Roentgen accidentally discovered

 In 1895

Etymology

Since these rays were new, and of unknown nature and origin therefore Wilhelm
Roentgen called them X-rays (X = unknown)

Production of X-Rays

 X-rays are produced in a cathode-ray tube when the electron beam (cathode
ray) falls on a metal target (anode).
 When an electron in the cathode ray hits a metal atom in the target, it can (if
it has sufficient energy) knock out an electron from an inner shell of the
atom.
 This produces a metal ion with an electron missing from an inner orbital
 The electronic configuration is unstable, and an electron from an orbital of
higher energy drops in to the half-filled orbital and a photon is emitted.
 The photon corresponds to electromagnetic radiations in the x-ray region.
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General Characteristics

 The X-rays are electromagnetic radiations.

 They have very high frequency depending upon the nature of anode target
 X-rays are emitted from the target in all directions. A small portion of them is
used for useful purpose through the windows
 The wavelength of X-rays produced depends upon the nature of target metal
 Every metal has its own characteristic X-rays
 They are highly penetrating

Atomic Number and X-rays

a) Introduction

 Moseley undertook a systematic and comprehensive study of X-rays in 1913

 His researches covered a range of wavelengths 0.04 - 0.08 Ao
 He used the technique of X-rays spectroscopy (just discovered by Max von
Laue) to determine the atomic numbers of the elements
b) Conclusions

Moseley made following conclusions from the detailed analysis of spectral lines
which he obtained from 38 different elements, (from Al to Au)

i) The frequencies of X-rays increase in a regular manner from one element to the
other in the Periodic Table.
ii) The frequencies of these rays are directly proportional to the no of protons in
the nucleus, called “atomic number”.

iii) The spectral lines could be classified into two distinct groups.

 K-series : contains shorter wavelengths

 L-series : contain longer wavelengths
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iv) If the target element is of higher atomic number the wave-length of X-rays
becomes shorter.

v) A relationship between frequency (𝑢) and atomic number (Z) of the elements is
given as;

This is called Moseley Law. Where a and b are called constant quantities. This law
states that the frequency of a spectral line in X-ray spectrum varies as the square
of atomic number of an element emitting it.

Uses of X-Rays

1) X-rays have different penetrating powers for different types of matter. X-rays
cannot pass through metals, but they can pass through plastic, leather etc. easily.
That’s why they can be used for security purposes to photograph interior of
objects.

2) They are used in medical radiography to locate fracture in the bones.

3) In England, in 1913 William Bragg and Lawrence Bragg used X-ray diffraction
(XRD) technique to study the crystal structure.

4) X-rays can be used to ionize gases.

THE QUANTUM NUMBERS AND ORBITALS

Introduction

 Schrodinger in 1926 gave an equation in which electrons are treated as

moving with wave like motion in the three dimensional space around the
nucleus.
 The solution of Schrodinger’s wave equation gives certain mathematical
integers. These sets of numerical values, which give the acceptable picture of
an atom, are called Quantum Numbers.
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 There are four quantum numbers which can describe the electron
completely

1) Principal Quantum No. (n)

 It determines the size of the orbit and the distance from the nucleus.
 Greater the distance from the nucleus, larger will be the size of the orbit

 The number of electrons accommodated in an orbit is given by 2n2

 The higher the value of n, the higher will be the energy of the electron and
space around the nucleus
 The circular path of an electron around the nucleus is called an orbit
 A cloud showing the probability of finding the electron in terms of charged
cloud around the nucleus is called Electron Cloud

2) The Azimuthal Quantum No. (𝑙)

 It describes the shape of an orbital

 Its value is always one less than that of value of n
 The various energy sub-levels (𝑙) are s, p, d, f having at the most 2, 6, 10 and
14 electrons in them respectively.
 They are designated as s for sharp, p for principal, d for diffused and f for
fundamental
 The values of 𝑙 are;

 The maximum number of electrons in a subshell are: 

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 The number of orbit gives the no of orbitals

 The shapes of orbitals described by Azimuthal Quantum number are

 s = spherical, p = dumbbell, d = sausage and f = complicated

3) Magnetic Quantum No. (m)

 It explains the effect of an orbital in the magnetic field

 Magnetic quantum number determines the orientation of orbital
 It is related with Azimuthal Quantum number as follows

 If l = o (s), m = o
 It means that an s-orbital is spherical in shape because it is not
deflected in any particular direction on placing in a magnetic field
 If l = 1 (p), m = + 1, 0, -1
 It means that a p-orbital can be deflected in three directions on
placing in a magnetic field, i.e. a p-orbital splits in to three
degenerate orbitals in a magnetic field
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 If f = 2 (d), then m = +2, + 1, 0, -1, -2

 It means that a d-orbital can be deflected in 5-directions on placing
in a magnetic field

 If l = 3 (f), then, m = + 3, + 2, +1, 0, -1, -2, -3

 An f—orbital can be deflected in 7- direction in a magnetic field.
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4) Spin Quantum Number (s)

 It describes the direction of spin of an electron

 In 1925 Goudsmit suggested that an electron while moving in an orbital
around the nucleus also rotates or spins about its own axis
 Spin may be clockwise or anticlockwise
 50 % chance of clockwise and 50% chance of anticlockwise 

ELECTRONIC CONFIGURATIONS

Definition

The representation of filling of electrons in different orbitals of an atom is called its

electronic configuration

The Relative Energies of Atomic Orbitals

 The relative energies depend upon the size of

the orbitals
s<p<d<f

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11th Chemistry| Chapter 2: Atomic Structure Notes Provided by TaleemCorner.com Page 29

 An orbital like s, px, py, pz, dxy etc. can have maximum two electrons

Rules for Distribution of Electrons in Different Orbitals

1) n + 𝑙 rule

 It gives energy order of orbitals

 It states that “An added electron will always enter in an orbit having lower n
+ 𝑙 value”

So, 2s-orbital is filled first because it has lower value of n + 𝑙 than that for 3d
orbital

 If n + 𝑙 values of two orbitals are same, then the orbital with lower n value
has lower energy and electron will be added to that orbital first

Here 3d orbital is filled first because the value of n for 3d is smaller than that of 4p

2) Auf-Bau Principle

 The electrons are placed in energy sub-levels in the order of increasing

energy values of sub-levels

3) Pauli’s Exclusion Principle

 According to it “No two electrons in the same orbital can have the same set
of four Quantum numbers
11th Chemistry| Chapter 2: Atomic Structure Notes Provided by TaleemCorner.com Page 30

Two electrons in same orbital have opposite spin

4) Hund’s Rule

 If degenerate orbitals are available for electrons, then electron would like to
live in separate orbitals and have rather parallel spin
 The Hund’s rule can be applied to predict the valency of an element because
the numbers of unpaired electrons give the valency of that element