Postulates of Dalton’s Atomic Theory

1. Matter is composed of extremely small indivisible particles called atoms.

2. An element consists of only one type of atoms. All the atoms of a particular element have identical properties
such as mass, shape, colour, density, chemical properties, etc.
3. All atoms of an element are identical, and different from those of other elements.
4. Atom is the smallest particle that takes part in chemical reactions.
5. Atoms can neither be created nor destroyed during chemical reactions.
6. Atoms of different elements may combine in a simple whole number ratio to form compound atoms or
molecules.
• Limitation of Dalton’s Atomic theory
1. The indivisibility of an atom was proved wrong: an atom can be further subdivided into protons, neutrons and
electrons.
2. According to Dalton, the atoms of same element are similar in all respects. However, atoms of same element
vary in their masses and densities. These atoms of different masses are called isotopes. For example, chlorine
has two isotopes with mass numbers 35 and 37.
3. Dalton also claimed that atoms of different elements are different in all respects. This has been proven wrong in
certain cases: argon and calcium atoms each have an atomic mass of 40 amu. These atoms are known as
isobars.
4. According to Dalton, atoms of different elements combine in simple whole number ratios to form compounds.
This is not observed in complex organic compounds like sugar (C12H22O11).
5. The theory fails to explain the existence of allotropes. it does not account for differences in properties of
charcoal, graphite, diamond.
 Ernest Rutherford Alpha particle experiment
In the alpha particle experiment, the effect of bombarding thin gold foil with alpha radiation
from radioactive substances (uranium) was observed. Alpha rays consist of positively charged
particles. He found that most of the alpha particles passed through a metal foil as though
nothing were there, but a few (about 1 in 8000) were scattered at large angles and sometimes
almost backward.
According to Rutherford’s model, most of the mass of the atom (99.95% or more) is
concentrated in a positively charged center, or nucleus, around which the negatively charged
electrons move. Although most of the mass of an atom is in its nucleus, the nucleus occupies
only a very small portion of the space of the atom. Nuclei have diameters of about 10-15 m,
whereas atomic diameters are about 10-10 m, a hundred thousand times larger.
The nuclear model easily explains the results of bombarding gold
with alpha particles. Alpha particles are much lighter than gold
atoms (196). (Alpha particles are helium nuclei(He2+)). Since most
of the alpha particles pass through the metal foil, so they are
undeflected by the lightweight electrons. When an alpha particle hit
the positively charged nucleus, it is either scattered at a wide angle
or deflected back by the massive, positively charged nucleus
 Rutherford’s Atomic theory
•Most of the part of an atom is empty.
•Approximately all the mass(99.95%) of the atom is concentrated at the center of atom which
is now called nucleus.
•The nucleus consists of positively charged particles and the total charge of the nucleus is
equal to Z.e, where Z is charge number, e is charge of proton.
•The negatively charged particles i.e. electrons revolve around the nucleus in different
circular orbits.
•Central region (nucleus) is very small in size with compared to the size of atom.
There were mainly two defects in Rutherford's atomic theory
Being a charged particle, electron must emit energy when it is accelerated, according to
classical electromagnetic theory. Hence it must radiate energy and due to continuous loss of
energy orbit of electron must decrease continuously. As a result electron will fall into the
nucleus eventually after some time. But this is against the practical situation.
1. If the electrons emit energy continuously, continuous spectrum should be formed. But in
practical line spectrum is observed.
 Bohr atomic theory
• Electrons revolve round the nucleus with constant velocities in
circular path situated at definite distances from the nucleus, this
circular path is called orbit . The energy of an electron in a
certain orbit remains constant. As long as it remains in that orbit,
it neither emits nor absorbs energy.
• According to Bohr the angular momentum of an electron is
quantized. Thus, the electrons can only move to those orbits
where its angular momentum is an integral multiple of h/2π,
where h is Planck’s constant. Thus, if m is mass of electron, v is Diagram of an electron
dropping from a higher orbital
velocity of electron, r is radius of that orbit, n is a simple to a lower one and emitting a
integer, then mvr = nh/2π. photon.
• When an electron transits from one energy level to another, it either emits or absorbs energy
which is equal to the difference between the two energy levels. If the energy of an electron
in the outer orbit (n2) is E2 = - RH/n2 and energy of electron in the inner orbit (n1) is E1 -
RH/n1 then E2 - E1 = ΔE = hν.
 Limitation of Bohr model
• Bohr model assumed that electrons have both a known radius and orbit. But according to
Heisenberg “The position and momentum of a particle cannot be simultaneously
measured with arbitrarily high precision”.
• Bohr model useful for predicting the behavior of electrons in hydrogen atoms but it fails
to explain the spectra of larger atoms and atoms have multiple electrons. The model also
didn’t work with neutral helium atoms.
• The Bohr model also could not account for the Zeeman effect, where spectral lines are
split into two or more in the presence of an external, static magnetic field.
 Radius of nth orbit
According to Bohr model, the attractive force between electron and nucleus is
balanced by centrifugal force of electron which is due to motion of electron and tend
to take electron away from nucleus. 𝑛2ℎ2
2 2 ………. (4)
Or, m𝑉 =2
Let’s assume, 4𝑚𝑟 𝜋
Atomic number of atom = Z From (3) and (4), we have
Charge on electron = e 𝑍𝑒2 𝑛2ℎ2
Charge on nucleus = Ze =
4π𝜖0 𝑟 4𝑚𝑟2𝜋2
Radius of nth orbit = r 2 2
𝑍𝑒 2 𝑛 ℎ
The electrostatic force of attraction = … (1) Or, 𝑟 = 2 for H , Z = 1, so
4π𝜖0 𝑟2 𝑍𝑚𝜋𝑒
𝑚𝑉2 𝜖0 𝑛2ℎ2
The centripetal force = … … . (2) 𝑟= ………..(5)
𝑟 𝑚𝜋𝑒2
Since both forces balanced each other. Hence 𝑟 = 𝑛2 × 0.529 Å imputing the
𝑚𝑉2
=
𝑍𝑒2
or m𝑉2 =
𝑍𝑒2
………..(3) values of h, m, e, 𝜖0 and π
𝑟 4π𝜖0 𝑟2 4π𝜖0 𝑟
𝑛ℎ Radius of an orbit is directly
Form Bohr postulate m𝑉𝑟 = proportional to the principal
2𝜋
𝑛2ℎ2 quantum number.
Or, m2𝑉2𝑟2 = 2
 Energy of electron in each orbit

For hydrogen
2
atom, the energy of the revolving
2
electron, E, is the sum of its kinetic
𝑚𝑉 𝑒
energy ( ) and potential energy (− ).
2 4π𝜖0 𝑟
𝑚𝑉2 𝑒2
𝐸= − -------(7)
2 4π𝜖0 𝑟
From equation (3), we have
𝑒2
𝑚𝑉2 = where Z = 1 for hydrogen atom.
4π𝜖0 𝑟
1 𝑒2 𝑒2 1 𝑒2
Thus, 𝐸= x − =− -------(8)
2 4π𝜖0 𝑟 4π𝜖0 𝑟 8 π𝜖0 𝑟
Substituting the values of r form equation 5, we get
𝑒2 𝑚𝜋𝑒2 𝑚𝑒4
𝐸=− × =− -------(9)
8𝜋𝜖0 𝜖0 𝑛 2 ℎ2 8𝜖0 2𝑛2 ℎ2
Now putting the value of m, π, e and h, we get,
1311.8
𝐸= − Kjmole-1-------(10)
𝑛2
Energy of an electron is inversely proportional to the principal quantum number.
 Wavelength of radiation and its relation with velocity
From Bohr model, We know that energy of the electron in orbit n1 and n2 is
𝑚𝑒4 𝑚𝑒4
𝐸1 = − 2 2 2
and 𝐸2 = −
8𝜖0 𝑛1 ℎ 8𝜖0 2𝑛22ℎ2
If electron transit from n2 and n1, then energy radiate is
𝑚𝑒4 1 1
∆𝐸 = 𝐸2 − 𝐸1 = − 2 ………….. (1)
8𝜖0 2ℎ2 𝑛12
𝑛2 n1 = 1, Lyman series,
According to Planck's equation
ℎ𝑐 n1 = 2, Balmer series,
∆𝐸 = ℎ𝜈 = ………….. (2)
𝜆 n1 = 3, Paschen series
From (1) and (2), we have
n1 = 4, Brackett series,
ℎ𝑐 𝑚𝑒4 1 1
= 2 2 2 − n1 = 5, Pfund series
𝜆 8𝜖0 ℎ 𝑛1 𝑛22
1 𝑚𝑒4 1 1
Or = − 2
𝜆 8𝑐𝜖0 2ℎ3 𝑛12 𝑛2
1 1 1 𝑚𝑒4
Or =RH 2 − 2 ………(3) Where, RH =
𝜆 𝑛1 𝑛2 8𝑐𝜖0 2ℎ3

RH is Rydberg constant. Imputing the Values e, m, h and c, the value of RH is found 109,679 cm-1
 Electron, Proton and neutron
An electron is a very light, negatively charged particle that exists in the region around the
atom’s positively charged nucleus.
A proton is a nuclear particle having a positive charge equal to that of the electron and a
mass more than 1800 times that of the electron.
The neutron is a nuclear particle having a mass almost identical to that of the proton but no
electric charge.

The atomic number (Z) is the number of protons in the nucleus of an atom.
The mass number (A) is the total number of protons and neutrons in a nucleus.
A nuclide is an atom characterized by a definite atomic number and mass number.
 Isotopes, isobar and isotones
Isotopes: The atoms having same atomic number but different atomic mass number are
called Isotope. E.g. 1H1, 1H2, 1H3 are all isotopes of hydrogen
Isobars: Nuclides having the same mass number but having the different Proton/Atomic
number are called Isobar.
Isotones: Atoms of different elements having different mass number and different atomic
number but same neutron number are called Isotones.

isobars

Heisenberg’s uncertainty principle states that it is impossible to know precisely and accurately
both the position and momentum of a particles simultaneously. It is also stated that the product
of the uncertainty in position and the uncertainty in momentum of a particle can be no smaller
than Planck’s constant divided by 4π . Thus, letting ∆ x be the uncertainty in the x coordinate of
the particle and letting ∆px be the uncertainty in the momentum in the x direction, we have
 Applicability of uncertainty principle
The uncertainty product is negligible in case of large objects. For a moving ball of iron weighing
500 g, the uncertainty expression assumes the form
ℎ ℎ 6.625 × 10−27
Δx × mΔν ≥ or, Δx × Δν ≥ ≈ ≈ 5 × 10-31 erg sec g–1
2π 4mπ 4 × 500 × 3.14
which is very small and thus negligible. Therefore for large objects, the uncertainty of
measurements is practically nil.
But for an electron of mass m = 9.109 × 10– 28 g, the product of the uncertainty of
measurements is quite large as
ℎ ℎ 6.625 × 10−27
Δx × mΔν ≥ or, Δx × Δν ≥ ≈ ≈ 0.3 erg sec g–1
2π 4mπ 4 ×9.109 × 10 × 3.14
– 28

This value is large enough in comparison with the size of the electron and is thus in no way
negligible. It is therefore very clear that the uncertainty principle is only important in
considering measurements of small particles comprising an atomic system.
 Louis de Broglie
Louis de Broglie reasoned that if light (considered as a wave) exhibits particle aspects, then
perhaps particles of matter show characteristics of waves under the proper circumstances. He
therefore postulated that a particle of matter of mass m and speed v has an associated
wavelength, by analogy with light:
ℎ
𝜆 =
mv
Derivation of de Broglie equation
According to Planck, The photon energy E is given by
𝐸 = ℎ𝜈------(1)
Where ℎ is the Planck’s constant, 𝜈 is the frequency of radiation. By applying Einstein’s mass-
energy relationship, the energy associated with photon of mass ‘m’ is given as
𝐸 = 𝑚𝑐2------(2)
Where c is the velocity of the radiation, From equation (1) and (2), we get
𝑐 𝑐 ℎ ℎ
𝑚𝑐2 = ℎ𝜈 = ℎ ∵𝜈= Or, 𝑝 = Or, Momentum =
𝜆 𝜆 𝜆 Wavelength
ℎ 1
Or, 𝑚𝑐 = Or, Momentum ∝ ………..(3),
𝜆 Wavelength
this equation (3) is called De Broglie equation.
 Applicability of Louis de Broglie equation
The de Broglie’s equation is not true for all particles, but it is only with very small particles,
such as electrons, that the wave-like aspect is of any significance. Large particles in motion
though possess wavelength, but it is not measurable or observable.
(a) For a large mass
Let us consider a stone of mass 100 g moving with a velocity of 1000 cm/sec. The de
Broglie’s wavelength λ will be given as follows :
ℎ 6.6256 × 10−27
𝜆 = = = 6.6256 × 10−32
mv 100 × 1000
This is too small to be measurable by any instrument and hence no significance.
(b) For a small mass
Let us now consider an electron in a hydrogen atom. It has a mass = 9.1091 × 10– 28 g and
moves with a velocity 2.188 × 10– 8 cm/sec. The de Broglie’s wavelength λ is given as
ℎ 6.6256 × 10−27
𝜆 = = = 3.32×10–8 cm
mv 9.1091×10 ×2.188×10
−28 −8
This value is quite comparable to the wavelength of X-rays and hence detectable. It is,
therefore, reasonable to expect from the above discussion that everything in nature
possesses both the properties of particles (or discrete units) and also the
properties of waves (or continuity).
 Quantum numbers
Quantum numbers
According to quantum mechanics, each electron in an atom is described by four different
quantum numbers, three of which (n, l, and ml) specify the wave function that gives the
probability of finding the electron at various points in space. A wave function for an
electron in an atom is called an atomic orbital.

1. Principal Quantum Number (n) This quantum number is the one on which the energy of
an electron in an atom principally depends; it can have any positive value: 1, 2, 3, and so on.
The energy of an electron in an atom depends principally on n. The smaller n is, the lower
the energy. The size of an orbital also depends on n. The larger the value of n is, the larger
the orbital. Orbitals of the same quantum state n are said to belong to the same shell. Shells
are sometimes designated by the following letters:
 Quantum Number
2. Angular Momentum Quantum Number (l) (Also Called Azimuthal Quantum Number)
This quantum number distinguishes orbitals of given n having different shapes; it can have
any integer value from 0 to n-1. Within each shell of quantum number n, there are n different
kinds of orbitals, each with a distinctive shape denoted by an l quantum number. For example,
if an electron has a principal quantum number of 3, the possible values for l are 0, 1, and 2.
Thus, within the M shell (n =3), there are three kinds of orbitals, each having a different shape
for the region where the electron is most likely to be found.
Although the energy of an orbital is principally determined by the n quantum number, the
energy also depends somewhat on the l quantum number (except for the H atom). For a given
n, the energy of an orbital increases with l.
Orbitals of the same n but different l are said to belong to different subshells of a given shell.
The different subshells are usually denoted by letters as follows:
 Quantum Number
3. Magnetic Quantum Number (l) This quantum number distinguishes orbitals of given n and
l—that is, of given energy and shape but having a different orientation in space; the allowed
values are the integers from -l to l. For l = 0 (s subshell), the allowed l quantum number is 0
only; there is only one orbital in the s subshell. For l =1 ( p subshell), l = -1, 0, and 1; there
are three different orbitals in the p subshell. The orbitals have the same shape but different
orientations in space. there are 2l +1 orbitals in each subshell of quantum number l.
4. Spin Quantum Number (s) This quantum number refers to the two possible orientations of
the spin axis of an electron; possible values are -1/2 and +1/2. An electron acts as though it
were spinning. Such an electron spin would give rise to a circulating electric charge that
would generate a magnetic field. In this way, an electron behaves like a small bar magnet
 Quantum Number
What is the total number of orbitals associated with the principal quantum number n = 4?
For n = 4, there are four possible values of azimuthal quantum number.
l = 0, 1, 2, and 3
Thus fourth energy level consists of four subshells or orbitals which are
designated as
4s, 4p, 4d and 4f.

Write the four quantum numbers for an electron in a 4p orbital.

For 4p,
Principal quantum number is n = 4
Since p subshell is represented by l = 1, thus for 4p the azimuthal quantum number is 1.
When l = 1, then, magnetic quantum number m = +1, 0, -1.

4p n l m s
+2, − 2
4 1 +1 1 1

+2, − 2
0 1 1

+2, − 2
-1 1 1
 Shape of the orbitals
Orbit: According to Bohr theory electron are revolved
around the nucleus in definite circular path with
certain energy. This circular path of electron is called
orbit.
Orbital: According to the quantum mechanical theory,
the three dimensional space around the nucleus of an
atom in which probability of finding the electrons are
maximum is called orbital.
 Schrödinger’s Wave Equation
c
The equation for the standing wave comparable with that of a stretched string is
𝑥
Ψ = A sin 2π ……….(1)
𝜆
where Ψ is a mathematical function representing the amplitude of wave, x is the displacement
in a given direction, and λ is the wavelength and A is a constant. Differentiating equation 1 2
times with respect to x we have
𝑑Ψ 2π 𝑥
=A cos 2π ……….(2) and
𝑑𝑥 𝜆 𝜆
𝑑2Ψ 4π2 𝑥 4π2
=-A Sin 2π = - Ψ……….(3)
𝑑𝑥2 𝜆2 𝜆 𝜆2
The K.E. 2of the
2 2
particle of mass m and velocity ν is given by the relation
𝑚𝑣 𝑚𝑣
K.E = = ……….(4)
2 2𝑚
According to Broglie’s equation
2 2
ℎ ℎ ℎ
λ= or λ2= 2 2 or 𝑚2𝑣2 = 2 …….(5)
𝑚𝑣 𝑚𝑣 λ
Putting the values of 𝑚2𝑣2 in equation (4), we get
1 ℎ2 1 ℎ2 𝑑2Ψ
K.E = × 2 =- × . 2 ( From equation 3, putting the values of 𝜆2)
2 mλ 2𝑚 4𝜋 Ψ 𝑑𝑥
2
 Schrödinger’s Wave Equation
ℎ2 𝑑2Ψ
K.E = - 2 . 2 ………(6)
8𝜋 mΨ 𝑑𝑥
Total energy is the sum of kinetic energy and potential energy
E = K.E + P.E
ℎ2 𝑑2Ψ
Or K.E = E- P.E = - 2 .
8𝜋 mΨ 𝑑𝑥2
𝑑2Ψ 8𝜋 2m
Or, 2 = - 2 (E- P.E)Ψ
𝑑𝑥 ℎ
2
𝑑 Ψ 8𝜋 m 2
Or, 2 + 2 (E- P.E)Ψ = 0……… (7)
𝑑𝑥 ℎ
This is Schrödinger’s equation in one dimension. It need be generalised for a particle whose
motion is described by three space coordinates x, y and z. Thus,
𝑑2Ψ 𝑑2Ψ 𝑑2Ψ 8𝜋 2m
2 + 2 + 2 + 2 (E- P.E)Ψ = 0 ………(8)
𝑑𝑥 𝑑𝑦 𝑑𝑧 ℎ
This equation is called the Schrödinger’s Wave Equation. The first three terms on the left-hand
side are represented by Δ2ψ.
2 8𝜋 2m
∆ Ψ+ 2 (E- P.E)Ψ = 0 ………(9)
ℎ
𝑑2 𝑑2 𝑑2
Where, ∆2 = + + 2 is called Laplacian Operator.
𝑑𝑥2 𝑑𝑦2 𝑑𝑧
 Significance of ψ and ψ2
Information about a particle in a given energy level is contained
in a mathematical expression called a wave function, ψ. Its
square, ψ2, gives the probability of finding the particle within a
region of space.
The wave function and its square, ψ2, have values for all
locations about a nucleus. Figure 1 shows values of ψ2 for the
electron in the lowest energy level of the hydrogen atom along a
line starting from the nucleus. Note that ψ2 is large near the
nucleus (r = 0), indicating that the electron is most likely to be
found in this region. The value of ψ2 decreases rapidly as the
distance from the nucleus increases, but ψ2 never goes to exactly Plot of ψ2 for the lowest
energy level of the hydrogen
zero, although the probability does become extremely small at
atom. The square of the wave
large distances from the nucleus. This means that an atom does function is plotted versus the
not have a definite boundary, unlike in the Bohr model of the distance, r, from the nucleus.
atom.