Atomic Structure

Md. Arif Hossain

B.Sc. and M.S (Applied Chemistry & Chemical Engineering, University of Dhaka)
Lecturer, Department of Chemistry
Dhaka University of Engineering & Technology, Gazipur
Email:[email protected]
[email protected]
Mobile number: +8801925802336
Matter and Atom:
Anything that has mass and occupies space is called matter.
A matter is made up of tiny particles. These particles are invisible to a naked eye.
These tiny particles which made elements are called atom.
An atom is the smallest unit of ordinary matter that forms a chemical element.
Atomic Model:
Rutherford Atomic Model and Limitations
Rutherford Atomic Model – The plum pudding model is given by J. J. Thomson
failed to explain certain experimental results associated with the atomic structure of
elements. Ernest Rutherford, a British scientist conducted an experiment and based
on the observations of this experiment, he proposed the atomic structure of elements
and gave Rutherford Atomic Model.
Rutherford’s Alpha Scattering Experiment
Rutherford‟s conducted an experiment by bombarding a thin sheet of gold with α-
particles and then studied the trajectory of these particles after their interaction with
the gold foil. Rutherford, in his experiment, directed high energy streams of α-
particles from a radioactive source at a thin sheet (100 nm thickness) of gold. In
order to study the deflection caused to the α-particles, he placed a fluorescent zinc
sulphide screen around the thin gold foil. Rutherford made certain observations that
contradicted Thomson‟s atomic model.
Observations of Rutherford’s Alpha Scattering Experiment
The observations made by Rutherford led him to conclude that:
1. A major fraction of the α-particles bombarded towards the gold sheet passed through it
without any deflection, and hence most of the space in an atom is empty.
2. Some of the α-particles were deflected by the gold sheet by very small angles, and hence
the positive charge in an atom is not uniformly distributed. The positive charge in an atom is
concentrated in a very small volume.
3. Very few of the α-particles were deflected back, that is only a few α-particles had nearly
1800 angle of deflection. So the volume occupied by the positively charged particles in an
atom is very small as compared to the total volume of an atom.
Rutherford Atomic Model
Based on the above observations and conclusions, Rutherford proposed the atomic
structure of elements. According to the Rutherford atomic model:
1. The positively charged particles and most of the mass of an atom was
concentrated in an extremely small volume. He called this region of the atom as a
nucleus.
2. Rutherford model proposed that the negatively charged electrons surround the
nucleus of an atom. He also claimed that the electrons surrounding the nucleus
revolve around it with very high speed in circular paths. He named these circular
paths as orbits.
3. Electrons being negatively charged and nucleus being a densely concentrated
mass of positively charged particles are held together by a strong electrostatic force
of attraction.
Limitations of Rutherford Atomic Model
Although the Rutherford atomic model was based on experimental observations it
failed to explain certain things.
1. Rutherford proposed that the electrons revolve around the nucleus in fixed paths
called orbits. According to Maxwell, accelerated charged particles emit
electromagnetic radiations and hence an electron revolving around the nucleus
should emit electromagnetic radiation. This radiation would carry energy from the
motion of the electron which would come at the cost of shrinking of orbits.
Ultimately the electrons would collapse in the nucleus. Calculations have shown that
as per the Rutherford model, an electron would collapse in the nucleus in less than
10-8 seconds. So Rutherford model was not in accordance with Maxwell’s theory
and could not explain the stability of an atom.
2. One of the drawbacks of the Rutherford model was also that he did not say
anything about the arrangement of electrons in an atom which made his theory
incomplete.
3. Although the early atomic models were inaccurate and failed to explain certain
experimental results, they were the base for future developments in the world of
quantum mechanics.
Bohr Model:
Postulates of Bohr’s Theory
(1) Electrons travel around the nucleus in specific permitted
circular orbits and in no others.
Electrons in each orbit have a definite energy and are at a fixed distance from the nucleus.
The orbits are given the letter designation n and each is numbered 1, 2, 3, etc. (or K, L, M,
etc.) as the distance from the nucleus increases.
(2) While in these specific orbits, an electron does not radiate (or lose) energy.
Therefore in each of these orbits the energy of an electron remains the same i.e. it neither
loses nor gains energy. Hence the specific orbits available to the electron in an atom are
referred to as stationary energy levels or simply energy levels.
(3) An electron can move from one energy level to another by quantum or photon jumps
only.
When an electron resides in the orbit which is lowest in energy (which is also closest to the
nucleus), the electron is said to be in the ground state. When an electron is supplied energy, it
absorbs one quantum or photon of energy and jumps to a higher energy level. The electron
then has potential energy and is said to be in an excited state.
The quantum or photon of energy absorbed or emitted is the difference between the lower
and higher energy levels of the atom
ΔE = Ehigh – Elow = hν ...(1)
where h is Planck‟s constant and ν the frequency of a photon emitted or absorbed energy.
(4) The angular momentum (mvr) of an electron orbiting around the nucleus is an
integral multiple of Planck’s constant divided by 2π.
𝑛ℎ
Angular momentum mvr = ...........(2)
2π
where m = mass of electron, v = velocity of the electron, r = radius of the orbit ; n = 1, 2, 3,
etc., and h = Planck‟s constant.
Limitations of Bohr’s Model of an Atom
1. Bohr‟s model of an atom failed to explain the Zeeman Effect (effect of
magnetic field on the spectra of atoms).
2. It also failed to explain the Stark effect (effect of electric field on the
spectra of atoms).
3. It violates the Heisenberg Uncertainty Principle.
4. It could not explain the spectra obtained from larger atoms
Atomic Number:
The atomic number or proton number (symbol Z) of a chemical element is the
number of protons found in the nucleus of every atom of that element. The atomic
number uniquely identifies a chemical element. It is identical to the charge number
of the nucleus. In a neutral atom, the atomic number is also equal to the number of
electrons.
Atomic Mass Number:
An element‟s mass number (A) is the sum of the number of protons and the number
of neutrons.
Example: An Aluminum atom has 13 proton
(atomic number) and 14 neutron. Therefore mass
number of the Aluminum atom is 27 and it represents
as 2713Al
Calculation of radius of orbits
Consider an electron of charge e revolving around a nucleus of hydrogen atom. Let m be the
mass of the electron, rn the radius of the orbit, and n the number of orbit.
ϵo𝑛2ℎ2
Therefore, radius of n orbit, rn = ...(1)
π𝑚𝑒2
Since the value of h, ϵo , m and e had been determined experimentally, substituting these
values in (1), we have
rn = n2 × 0.529 × 10–10 m ...(2)
where n is the principal quantum number and hence the number of the orbit.
When n = 1, the equation (2) becomes r1 = 0.529 × 10–10 m = α0
This last quantity, α0 called the first Bohr radius was taken by Bohr to be the radius of the
hydrogen atom in the ground state.
Calculation of energy of orbits
Consider an electron of charge e revolving around a nucleus of hydrogen atom. Let m be the
mass of the electron, r the radius of the orbit and n the number of orbit.
𝑚𝑒4
Therefore, energy of n orbit En = - ...(1)
8ϵo2𝑛2ℎ2
Since the value of h, ϵo, m and e had been determined experimentally, substituting these
values in (1) , we have
13.6
En = - eV …..(2)
𝑛2
where n is the principal quantum number and hence the number of the orbit.
When n = 1, the equation (2) becomes E1 = - 13.6 eV
Significance of Negative Value of Energy
The energy of an electron at infinity is arbitrarily assumed to be zero. This state is called
zero-energy state. When an electron moves and comes under the influence of nucleus, it does
some work and spends its energy in this process. Thus the energy of the electron decreases
and it becomes less than zero i.e. it acquires a negative value.
Electromagnetic radiation
Visible light
Hydrogen emission spectrum
We all know that electrons in an atom or a molecule absorb energy and get excited,
they jump from lower energy level to higher energy level, and they emit radiations
when they come back to their original states. This phenomenon accounts for the
emission spectrum through hydrogen too, better known as hydrogen emission
spectrum. When an electric discharge is passed through a gaseous hydrogen
molecule, the hydrogen atoms in the molecule dissociate. This leads to the emission
of electromagnetic radiation by the energetically excited hydrogen atoms. The
hydrogen emission spectrum consists of radiations of discrete frequencies. These
series of radiations are named after the scientists who discovered them.
The formula for correlating the wave length of the spectral lines emitted and the
energy shells involved. This formula is given as:
1 1 1
= RH ( 2 - )
λ 𝑛1 𝑛22
Where,
n1 and n2 are integers and n2 is always greater than n1.
RH is constant, called Rydberg constant
• Transition from the first shell to any other shell – Lyman series
• Transition from the second shell to any other shell – Balmer series
• Transition from the third shell to any other shell – Paschen series
• Transition from the fourth shell to any other shell – Bracket series
• Transition from the fifth shell to any other shell – Pfund series
ℎ𝑐 1 1
Therefore Energy ΔE = = h*c*RH ( 2 - )
λ 𝑛1 𝑛22
Where,
n1 and n2 are integers and n2 is always greater than n1.
RH is constant, called Rydberg constant. RH = 109678 cm-1
h= Planck's constant
c= Velocity of light
λ= Wave length of light
Isotopes:
Atoms having the same number of protons but different number of neutrons are
isotopes.
For example, the two isotopes of Uranium are, , 23592 U and 23992 U. You will see here
that the number of protons is the same in both the isotopes, but they contain 143 and
147 neutrons respectively. The presence of an extra neutron significantly changes the
behavior of that particular atom. There are two different types of isotopes, stable and
radioactive. Stable isotopes are one that can exist in its free state without breaking
down spontaneously. Radioactive isotopes are ones that are too unstable to sustain
itself, and they spontaneously break down into two lighter daughter elements with the
emission of particles such as alpha, beta, and gamma rays.
Isotones:
Atoms having the same number of neutrons but a different number of protons are
isotones.
For example, 3616S, 3717Cl, 3818Ar, 3919K, and 4020Ca are all isotones of 20 since they all
contain 20 neutrons.
Isobars:
Atoms having the same mass number (A) are isobars. The series of elements with
40 Mass numbers serve as a good example; 4018Ar, 4019K, and 4020Ca. The nucleus of
all the above-mentioned elements contain the same number of particles in the
nucleus but contain varying numbers of protons and neutrons.
Orbit:
An orbit is the fixed path along which electrons revolve around the nucleus of the
atom. Thus, all atoms particularly revolve in an orbit.

Figure: Orbit of an atom

Orbital:
A mathematical equation which defines a volume of space in which there is a specified
probability of finding an electron of a specified energy.
Types of Orbitals
Below we will look at some of the common types of orbitals and discuss a few things about
orbital shapes.
s Orbital
S orbital is spherically symmetrical orbital around the atomic nucleus.
p Orbital
The p orbitals are dumbbell-shaped. The node in the p orbital occurs at the
center of the nucleus. The p orbital can occupy a maximum of six electrons
due to the presence of three orbitals. The three p orbitals are oriented right Figure: S orbital
angles to each other.
As the lobes lie along one of the x, y or z-axis, these three orbitals are given the
designations px, py, and pz. Thus, we can say that there are three p orbitals whose
axes are mutually perpendicular.

Figure: px, py, and pz Orbital

d orbital
The d orbital is cloverleaf or two dumbbells in a plane. there are five d orbitals. The
five d-orbitals are assigned with the designation dxy, dyz, dxz, dx 2–y 2 and dz 2. The
energy of all five orbitals are equal but the first four orbitals are similar in shape to
each other while the dz2 differ from others.
 Figure: Five d orbitals
f Orbital
f orbital has diffused shape.
The sequence for the f block is unique. Beginning with lanthanum (Z=57) it starts
a block that contains 15 elements.
What are Quantum Numbers?
The set of numbers used to describe the position and energy of the electron in an atom
are called quantum numbers. There are four quantum numbers, namely, principal,
azimuthal, magnetic and spin quantum numbers.
Principal Quantum Number (n = 1, 2, 3, 4, …∞)
The principle quantum number describes the electron shell, or energy level, of an
electron. The principal quantum number, n, defines the energy level or shell of the
electron. It is the first quantum number that must be determined, as it defines the
available values for all other quantum numbers. Think of Bohr‟s model for the atom; n
defines the ring on which the electron resides.
Azimuthal (Angular Momentum) Quantum Number (l = 0, 1, 2, …(n-1) )
The azimuthal quantum number, also known as the (angular quantum number or orbital
quantum number), describes the subshell. The azimuthal, or angular momentum,
quantum number, l, defines the type or shape of the orbital where the electron most
probably resides. It is the second quantum number to be determined as its value relies
only on n (i.e., if n = 2, then l = 0 or 1 since n – 1 = 1)..
If l = 0, the electron is in an s-orbital.
If l = 1, the electron is in a p-orbital.
If l = 2, the electron is in a d-orbital.
If l = 3, the electron is in an f-orbital
Magnetic Quantum Number (ml = -l…0…+l)
The magnetic quantum number describes the specific orbital (or "cloud") within that
subshell, and yields the projection of the orbital angular momentum along a
specified axis. The magnetic quantum number, ml, defines the orientation of the
orbital in which the electron inhabits. The number of ml values is called the
degeneracy, or the number of orbitals in the atom that are at the same energy level.
For an s-orbital, ml = 0, and degeneracy = 1.
For a p-orbital, ml = -1, 0, +1, and degeneracy = 3.
For a d-orbital, ml = -2, -1, 0, +1, +2, and degeneracy = 5.
For an f-orbital, ml = -3, -2, -1, 0, +1, +2, +3, and degeneracy = 7
Spin Quantum Number (ms = - ½, + ½)
The spin quantum number describes the intrinsic spin of the electron within each orbital and
gives the projection of the spin angular momentum ms along the specified axis. The spin
quantum number, ms, is completely independent of the values of n, l, and ml. It is always +
½ for an electron who has its spin oriented up, and – ½ for an electron who has its spin
oriented down. This means that there are only two electrons allowed per orbital, no matter
the energy level, shape, or orientation.
Electronic configuration of elements:
The electron configuration of an element describes how electrons are distributed in
its atomic orbitals. Electron configurations of atoms follow a standard notation in
which all electron-containing atomic subshells (with the number of electrons they
hold written in superscript) are placed in a sequence. For example, the electron
configuration of sodium is 1s22s22p63s1.
Filling of Atomic Orbitals
Aufbau Principle
This principle is named after the German word „Aufbeen‟ which means „build up‟.
The Aufbau principle dictates that electrons will occupy the orbitals having lower
energies before occupying higher energy orbitals.
The energy of an orbital is calculated by the sum of the principal and the azimuthal
quantum numbers.
According to this principle, electrons are filled in the following order: 1s, 2s, 2p, 3s,
3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p…
The order in which electrons are filled in atomic orbitals as per the Aufbau principle is
illustrated below.

It is important to note that there

exist many exceptions to the
Aufbau principle such as
chromium and copper. These
exceptions can sometimes be
explained by the stability
provided by half-filled or
completely filled subshells.
Pauli Exclusion Principle
The Pauli exclusion principle states that a maximum of two electrons, each having
opposite spins, can fit in an orbital.
This principle can also be stated as “no two electrons in the same atom have the
same values for all four quantum numbers”.
Therefore, if the principal, azimuthal, and magnetic numbers are the same for two
electrons, they must have opposite spins.
Hund’s Rule
This rule describes the order in which electrons are filled in all the orbitals
belonging to a subshell.
It states that every orbital in a given subshell is singly occupied by electrons
before a second electron is filled in an orbital.
In order to maximize the total spin, the electrons in the orbitals that only contain
one electron all have the same spin (or the same values of the spin quantum
number).
Thank You