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Atomic Theory and Structure of atom
Discovery of Electrons,Properties of Cathode Rays, Characteristics of an electron, Discovery of
Proton, Goldstein’s experiment’ Properties of Anode rays (Canal Rays), Discovery of Neutron, Atomic
structure- Postulates of Daltons atomic theory, Thomson’s Model of an Atom, .Rutherford’s Model of
an Atom & its drawbacks, Bohr’s Model of an Atom & limitations, Bohr’s model of atom revisited,
Atomic spectrum of hydrogen, Merits of Bohr’s atomic model,, Arrangement of electrons in the atoms,
Atomic orbitals - Quantum Numbers- Principal quantum number, Azimuthal quantum number
magnetic quantum number, spin quantum number, Electronic Configuration of Atoms of Elements -
Aufbau principle, Pauli’s Exclusion principle, Hund’s Rule Shape of orbitals - s,p. -Valence electrons,
Atomic Number, Mass Number, Isotopes, Isobars, Isotones, Representation of an element.
Learning Outcome
At the end of the unit the student must be able to
• Know the properties of electron, proton, and neutron.
• Understand Dalton’s Atomic theory and its draw backs
• Understand Thomson’s model of an atom
• Explain Rutherford’s model of an atom and its draw backs
• Describe Bohr’s model of an atom and its limitations
• Explain Atomic spectrum of hydrogen
• Give the arrangement of electrons in the atom
• Know the various atomic orbitals and their quantum numbers such as principal quantum number,
magnetic quantum number, spin quantum number
• Explain electronic configuration of atoms of first 20 elements.
• Know principals and rules which provide guidance to write electronic configuration - Aufbau
principle, Pauli’s Exclusion principle, Hund’s Rule.
• Understand various shapes of orbitals- s, p
• Understand the terms valence electron, atomic number, atomic mass , Isotopes, Isobars,
Isotones,
• Represent an element with nucleon and proton
John Dalton in 1808, proposed his famous atomic theory. He defined atom as the smallest
chemically indivisible particle of an element which cannot exist free. They exist in combination with
the same element or another element. Atoms are the building blocks of all the matter around us.
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Extensive research has been done to understand the composition of matter in the twentieth century
by J .J. Thomson, Rutherford, Neils Bohr, Chadwick and many other scientists. All these led to
the conclusion that Dalton’s concept “an atom is indivisible” is not correct. Atoms are found to be
made up of electrons, protons and neutrons. These are known as sub-atomic particles.
Anode
To vacuum pump
− + High voltage
generator
This experiment reveals that the rays which are emitted by the cathode are called cathode rays.
These rays travel from cathode to anode in the form of streaks of light. The cathode rays bombard
the glass which results in the glowing of the tube.
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1.1.2. Properties of Cathode Rays
The important properties of cathode rays are:
1.1.2.1. They travel in straight line: This is proved by the following experiment. When an opaque object
is placed in the path of cathode rays in a discharge tube, a shadow of the object appears at the
end of the cathode.
Cathode
Cathode rays
−
+
Anode
Shadow of the
(Metal cross)
metal cross
Figure 2. Cathode rays cast shadows of the object places in their path
1.1.2.2. Cathode rays are a beam of particles having mass and kinetic energy:
A paddle wheel placed in the path of the cathode rays, rotates. This is possible only when the
cathode rays consist of particles moving with certain velocity. i.e., they have mass and kinetic energy.
Light paddle
Cathode wheel Anode
Cathode rays
Figure 3. Cathode rays can rotate a light paddle wheel placed in their path
1.1.2.3. Cathode rays are negatively charged: When an electric field is applied in the path of cathode
rays, they get deflected towards the positive plate of the electric field.
Cathode Anode
− − − −
− − −
−
−
Cathode rays −
Electric field +
This shows that the cathode ray particles are negatively charged. Cathode rays are also deflected
by magnetic field.
1.1.2.4. Cathode ray beam deviated from its path in the presence of a magnetic field:
When magnetic field is applied perpendicular to the path of cathode rays the beam gets deflected
towards a pole.
Discharge tube
Cathode
Switch
1.1.2.5. The nature of the cathode rays are independent of the nature of the
gas taken in the discharge tube: This means that the same type of rays
with similar mass and charge having similar properties are produced In which metal
irrespective of the nature of the gas (i.e., H2 (or) O2 or Cl2 or any gas) atom did
taken in the tube. Rutherford
discover the
nucleus?
1.1.3. Characteristics of an electron
1. An electron is a negatively charged particles.
1
2. The mass of an electron is of a hydrogen atom. The absolute mass of an electron is 9
1840
× 10–28 g.
3. The relative charge of an electron is –1. The absolute charge is 1.6 × 10–19 coulombs. (It has
been found that this is the smallest negative charge carried by the particle).
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Perforated Anode
cathode
To vacuum pump
− + High voltage
generator
Figure 6. Production of anode rays or positive rays.
When very high voltage (about 10,000 volts) is applied to the discharge tube containing air at
about 0.001mm Hg a faint glow is obtained behind the cathode. (See figure 6 above)
These rays are believed to emanate from the anode, moving in the direction opposite to the
cathode rays. Hence, these rays are known as anode rays or positive rays.
About 30 years after the discovery of the electron, Irene Juliet-Curie (the daughter of the famous
scientists Marie and Pierre Curie) discovered that when alpha particles hit a sample of beryllium,
a beam that could go through almost anything was produced. The British scientist James
Chadwick found that this beam was not deflected by electric or magnetic fields. He concluded
that the particles carried no electric charge. Further investigation showed that these neutral
particles, which were named neutrons are part of all atomic nuclei (except the nuclei of most
hydrogen atoms). In general, a neutron is represented as ‘n’. The mass of an atom is therefore
given by the sum of the masses of protons and neutrons present in the nucleus.
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−
− − Positive sphere
−
− −
−
− − Electron
−
1. An atom consists of a positively charged sphere and the electrons are embedded in it.
(Figure 8)
2. The negative and positive charges are equal in magnitude. So, the atom as a whole is
electrically neutral (Figure 9).
Although Thomson’s model explained that atoms are electrically neutral, the results of
experiments carried out by other scientists could not be explained by this model,
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1.5.2. Rutherford’s Model of an Atom
Ernest Rutherford was interested in knowing how the electrons are arranged within an atom.
Rutherford designed an experiment for this. In this experiment, fast moving alpha (α )-particles
were made to fall on a thin gold foil.
• He selected a gold foil because he wanted a layer as thin as possible. This gold foil was
about 1000 atoms thick.
• α -particles are doubly charged helium ions. Since they have a mass of 4 u, the fast
moving α -particles have a considerable amount of energy.
• It was expected that α -particles would be deflected by the sub-atomic particles in the
gold atoms. Since the α -particles were much heavier than the protons, he did not expect to
see large deflections.
But, the α -particle scattering experiment gave totally unexpected results. The following
observations were made:
(iii) Most of the fast moving α -particles passed straight through the gold foil.
(ii) Some of the α -particles were deflected by the foil by small angles.
(iii) Surprisingly one out of every 12000 particles appeared to rebound.
In the words of Rutherford, “This result was almost an incredible as if you fire a 15-inch shell at a
piece of tissue paper and it comes back and hits you”.
Activity Let us think of an activity in an open field to understand the implications of this experiment. Let a
child stand in front of a wall with his eyes closed. Let him throw stones at the wall from a
distance. He will hear a sound when each stone strikes the wall. If he repeats this ten times, he
will hear the sound ten times. But if a blind-folded child were to throw stones at a barbed-wire
fence, most of the stones would not hit the fencing and no sound would be heard. This is
because there are lot of gaps in the fence which allow the stone to pass through them.
Following a similar reasoning, Rutherford concluded from the α -particle scattering experiment that
(i) Most of the space inside the atom is empty because most of the α -particles passed through
the gold foil without getting deflected.
(ii) Very few particles were deflected from their path indicating that the positive charge of the
atom occupies very little space.
(iii) A very small fraction of α -particles were deflected by 180°, indicating that all the positive
charge and mass of the gold atom were concentrated in a very small volume within the atom.
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From the data he also calculated that the radius of the nucleus is about 10 5 times less than the
radius of the atom.
On the basis of his experiment, Rutherford put forward the nuclear model of an atom which had
the following features.
(i) There is a positively charged centre in an atom called the nucleus. Nearly all the mass of an
atom resides in the nucleus.
(ii) The electrons revolve around the nucleus in well-defined orbits.
(iii) The size of the nucleus is very small as compared to the size of the atom.
N shell (n = 4)
M shell (n = 3)
L shell (n = 2)
K shell (n = 1)
Nucleus
Though Bohr model explains the stability of the atom, it could not explain certain experimental
observations viz., the atomic spectrum of atoms other than hydrogen. For the present, it is suffice
to know that Bohr model cannot explain the present day understanding of the atom. However, it
should be appreciated, that the Bohr model provided the basic structure to understand the
arrangement of electrons, protons and neutrons in an atom.
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increases as it moves away from the nucleus. The number of electrons in an energy level is given
by the formula 2n2, where ‘n’ is the number of the orbit. Thus for
K shell = n = 1 and no. of electrons = 2
This means that the first energy level nearer to the nucleus can hold a maximum of two electrons.
The next energy level (L shell)for which n =2, can hold a maximum of 8 electrons. The next higher
energy level i.e., the M shell for which n =3, can hold a maximum of 18 electrons and so on.
Nucleus
5
4
3
2
1
+
Energy levels
K L M N O
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Phosphorus P 15 2,8,5 1s2, 2s22p6, 3s23p3
Sulphur S 16 2,8,6 1a2,2s22p6, 3s23p4
Chlorine Cl 17 2,8,7 1s2, 2s22p63s23p5
Argon Ar 18 2,8,8 1s2, 2s22p6,3s23p6
Potassium K 19 2,8,8,1 1s2, 2s2 2p6, 3s23p6,4s1
Calcium Ca 20 2,8,8,2 1s2,2s22p6, 3s23p6,4s2
We will proceed to consider the changes brought about to Bohr’s model without going into the
details of the above stated reasons.
The path of an electron around the nucleus is no longer a definite path or orbit as conceived by
Bohr. It is called orbital.
An atomic orbital is defined as three dimensional space or region around the nucleus in which
the probability of finding the electron is maximum.
Bohr’s model of atom underwent a lot of changes and a Quantum mechanical model involving
atomic orbitals was evolved.
Bohr called his permitted orbits or stationary states as shells and named them K, L, M,
N………..etc., These are given numbers 1, 2, 3, 4…………etc., Each shell contains one or more
sub-shells or orbitals.
The number of sub shells is equal to the number of the shell.
The maximum number of electrons that can be accommodated in a shell is given by 2n 2 where n
is the number of the shell (1, 2, 3 …….etc) So the maximum number of electrons that can be
accommodated in
K shell (n = 1) 2 × 12 = 2
L shell (n = 2) 2 × 22 = 8
M shell (n = 3) 2 × 32 = 18
N shell (n = 4) 2 × 42 = 32.
Orbit Orbital
1. It is a definite path around the It is a region or space around the nucleus
nucleus along which the electron where the probability of finding the electron is
moves. maximum
2. It represents movement of electron It represents three dimensional space around
in one plane. the nucleus
3. Its shape is circular. Its shape may be spherical (for s orbital) dumb-
bell (p-orbitals) or any other shape (d, f)
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4. The position and velocity of the It is impossible to determine the position and
electron can be found precisely at velocity of electron at any instant with certainty.
any instant.
Table 3 Differences between orbit and orbital
In an atom, the state of each electron is different with respect to the nucleus. In order to define
the state of the electron completely, four quantum numbers are used.
They are
(a) Principal quantum number (n)
(b) Azimuthal quantum numbers ()
(c) Magnetic quantum number (m)
(d) Spin quantum number (s)
3. The value = 0 denotes that the electron is in the sub shell or s orbital.
The value = 1 denotes that the electron is in the p sub shell or p orbital.
The value = 2 denotes that the electron is in the d sub shell or d orbital
The value = 3 denotes that the electron is in the f sub shell or f orbital
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n=2 = 0; (2s) m=0
L shell = 1; (2p) m = –1, 0, +1 2 × 22 = 8
n=3 = 0; (3s) m=0
M shell = 2; (3p) m = –1, 0, +1 2 × 32 = 18
= 0; (4s) m=0
= 1; (4s) m=0
n=4 = 1; (4p) m = –1, 0, +1
N shell = 2; (4d) m = –2, –1, 0, +1, +2 2 × 42 = 32
= 3; (4f) m = –3, –2, –1, 0, +1, +2, +3
1.7.1. Principles and rules which provide guidance to write the electronic configuration.
The electronic configuration of an atom is written using the guidelines of the following principles
and rules.
1. Aufbau principle
2. Pauli’s exclusion principle.
3. Hund’s rule
Rule 1: The electrons first occupy that orbital for which (n + ) value is lowest.
Rule 2: When (n + ) values for two orbitals are equal, then the electrons first occupy the orbital
with lower value of n.
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p
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“In an atom no two electrons can have the same set of four quantum numbers”.
Illustration of Pauli’s exclusion principle
1. In an atom if one electron is assigned a set of four quantum numbers n = 1, = 0, m = 0,
1
s = + , then other electrons cannot be assigned the same set of quantum numbers.
2
2. If three quantum numbers for two electrons are the same, then these electrons must have
different fourth quantum number.
n l m s
1
First electron 1 0 0 +
2
1
Second electron 1 0 0 − Different
2
1.8.1. Illustration
In Hydrogen atom, there is only one electron which occupies 1s orbital and the electronic state
is represented by
1s 1s
Hydrogen 1s1 ↑ Helum 1s2 ↑↓
The third electron in Lithium would occupy 2s orbital which has the minimum energy in this shell.
In the atom beryllium, the fourth electron completes the 2s orbital and thus with boron, the fifth
electron must enter 2ps orbital.
1s 2s 2px 2p y 2pz
Lithium 1s2 2s1 ↑↓ ↑
1.9.2. p orbitals
1. p-orbital has three orientations i.e., probability of finding p-electron is along mutually
perpendicular X, Y and Z axis. These orbitals are thus named as px, py and pz orbital.
2. In px orbital, the electron density is distributed along X-axis while in p y and pz orbitals, the
electron density distribution are along Y and Z axes respectively.
3. Each p orbital is dumb bell shaped and consists of two lobes of electron cloud which extend
outwards and away from the nucleus along the axial line.
4. A nodal plane exists between the two lobes. Along this plane, the probability of finding
electron (Ψ 2) is zero and consequently the electron density is also zero.
5. In each p orbital, the point at which the two lobes meet together is a nodal point. It is the point
from which the nodal plane passes. The shapes of 2px, 2py and 2pz orbitals are shown below.
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Electronic configuration not only gives the arrangement of electrons outside the nucleus but
also gives the number of valence electrons. This number decides the chemical reactivity. Atoms
combine with one another to attain eight electrons in the valence shell which is the noble gas
configuration. This is achieved by lending, borrowing or sharing the valence electrons among
the atoms.
The number of valence electrons of an atom is called the valency (or maximum valency) of the
element.
Examples
(i) Oxygen has the electronic configuration 1s2, 2s2, 2p4. It has 6 electrons in its valence shell.
It can borrow 2 electrons to make it 8 so that it gets the configuration of neon. Hence the
valency of oxygen is 2.
(ii) Sulfur which has the configuration similar to oxygen as 1s2, 2s22p6, 3s23p4 also has 6
electrons in its valence shell. Its valency is 2 and maximum valency is 6.
(iii) Potassium has the configuration 1s2, 2s22p6, 3s23p64s1. By losing one electron from its
fourth shell it gets an outermost shell of 8 electrons and gets the configuration of Argon.
Hence its valency is 1.
(iv) Helium has 1s2 which is the maximum number of electrons for the first shell. It is considered
stable electronic configuration. Hence it has no reactivity.
(v) Neon and argon have 8 electrons in their valence shells. Hence these are also chemically
inert.
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present in the nucleus of an atom. In the notation for an atom, the atomic number, mass number
and symbol of the element are to be written as
Mass Number
Symbol of Distinguish
element between atomic
Atomic Number number and
14
For example, nitrogen is written as 7 N mass number
Solution a) Sodium has atomic number (Z) 11 and mass number 23.
Number of protons = Z = 11
Number of electrons = Z = 11
Number of neutrons = A-Z = 23 – 11 = 12
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In 1913, Soddy was the first to notice the presence two atoms of lead with same atomic number
but different mass number. He coined the word isotopes for them. Isotopes are atoms of the
same element having the same atomic number but different mass number
Isotopes are defined as the atoms of the same element, having the same atomic number
but different mass numbers..
1
For example, take the case of hydrogen atom, it has three atomic species namely protium 1H , ( )
deuterium ( 2
1 )
H or D and tritium ( 3
1 )
H or T .
The atomic number of each one is 1, but the mass number is 1, 2 and 3 respectively. Other such
12 14 35 37
examples are (i) carbon, 6 C and 6 C , (ii) chlorine, 17 Cl and 17 Cl , etc.,
Many elements consist of a mixture of isotopes. Each isotope of an element is a pure substance.
The chemical properties of isotopes are similar but their physical properties are different.
Chlorine occurs in nature in two isotopic forms, with masses 35 u and 37 u in the ratio of 3 : 1.
Obviously, the question arises: What should we take as the mass of chlorine atom? Let us find
out.
The mass of an atom of any natural element is taken as the average mass of all the naturally
occurring atoms of that element. If an element has no isotopes, then the mass of its atom would
be the same as the sum of protons and neutrons in it. But if an element occurs in isotopic forms,
then we have to know the percentage of each isotopic form and then the average mass is
calculated.
The average atomic mass of chlorine atom, on the basis of above data, will be
75 25
35 × 100 + 37 × 100
105 37 142
= + = = 35.5 u
4 4 4
This does not mean that any one atom of chlorine has a fractional mass of 35.5 u. It means that if
you take a certain amount of chlorine, it will contain both isotopes of chlorine and the average
mass is 35.5 u.
1.12.2. Examples
(i) Hydrogen exists as three isotopes – hydrogen, deuterium and tritium. All the three have the
same atomic number (1) but mass numbers as 1,2,3 respectively. These can be represented
as 1H1, 1H2 or 1D2 , 1H3 or 1T3
(ii) Chlorine has two isotopes with atomic number 17 and mass numbers 35 and 37. 17Cl35, 17Cl37
(iii) Carbon isotopes are 6C12, 6C13 and 6C14
(iv) Oxygen isotopes are 8O16, 8O17, 8O18
(v) Uranium isotopes are 92U234, 92U235, 92U238, 92U239
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1.12.3. Characteristics of isotopes
• Isotopes have the same number of protons and electrons, but different number of
neutrons.
• Since the isotopes have the same number of electrons they have the same electronic
configuration and possess same chemical properties.
• Isotopes differ in physical properties.
• Since isotopes have same electronic configuration their position in the periodic table is
also the same.
• All isotopes need not be radioactive . There are non- radioactive isotopes also. (eg)
Deuterium.
• Isotopes are identified by the instrument – mass spectrograph.
Mass number which is the sum of the number of protons and number of neutrons is a whole
number but atomic weight can be whole number or fractional. It is due to the presence of
isotopes. The relative atomic mass or relative atomic weight is the average of the mass number
of the isotopes based on their relative abundance.
1.12.4. Isobars
Atoms of same mass number but different atomic numbers are called isobars.
Since atomic numbers are different , isobars are atoms of different elements.
Isobars have different number of protons and electrons but same number of nucleons
1.12.5. Isotones
Atoms having same number of neutrons but different mass numbers are called isotones.
1.12.6. Applications
Since the chemical properties of all the isotopes of an element are the same, normally we are not
concerned about taking a mixture. But some isotopes have special properties which find them
useful in various fields. Some of them are:
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