Bangladesh Army University of Engineering & Technology

(BAUET)
Department of Mechanical Engineering
Qadirabad, Natore-6431.

Course Information
Course Code: CHEM-1113
Course Title: Quantitative Inorganic Chemistry
Year/Semester: 1st Year/1st Semester
Course Credit : 3
Contact Hour(s): 3/Week
Academic Session: Fall 2024
 Course Instructor
Name: Toshar Hossain
Designation: Lecturer, Dept. of Chemistry
Room No.: N-405
Contact:+8801787516691
Email: [email protected]
Marks Distribution:
Individual student will be evaluated based on the following criteria-
Category Marks
Class Participation/ Observation 5
Mid term 20
Class Test/ Assignments 15
Semester final Exam 60
Total = 100
Evaluation Policy (Grading System):

Numerical Markings Letter Grade Grade Points

80% and above A+ 4.00
75% to below 80% A 3.75
70% to below 75% A- 3.50
65% to below 70% B+ 3.25
60% to below 65% В 3.00
55% to below 60% B- 2.75
50% to below 55% C+ 2.50
45% to below 50% С 2.25
40%to below 45% D 2.00
Below 40% F* 0.00
Incomplete I -
(Assigned Courses are not
Appeared)
Course Objective(s):
1. To make able to use the idea about elements, structure properties
relationship to engineering sector.
2. To achieve fundamental knowledge of basic science of chemistry.
3. To study the different theorems of Chemistry and apply those
theorems in developing various instruments.
Course Learning Outcomes (CLOs):
On successful completion of this course, students will be able to-
Understand the fundamental knowledge of chemistry and the impact
CLO 1 of molecular structure of atoms on engineering science
Apply different laws and theorems of Chemistry to solve various
CLO 2 engineering problems.
Analyze and solve the chemical principles and process to be used in
CLO 3 engineering science
Course Content(s)/Syllabus:
Atomic structure: Structure of atom and its important theory, various atomic spectrums,
Planck’s Quantum theory, Quantum number, Electronic configuration and its uses.
Chemical bonds: Concept of chemical bonds(types, Properties, Lewis theory, VBT, MOT),
Hybridization, VSEPR theory.
Phase rule: Phase diagram of mono component system
Chemical Kinetics: Rate of reactions, Chemical equilibrium, Le-Chatelier's
principle, kp, kc
Acids and Bases,
Periodic classification of elements.
Organic Compound and Polymer.
Thermodynamics
Liquid state, Solution and Colligative properties.
Recommended Readings/Text Books:
S. Z. Haider Introduction to Modern Inorganic
Chemistry

R. D. Madan Modern Inorganic Chemistry

B. S. Bahl & Arun Bahl Advanced Organic Chemistry

S. Z. Haider Introduction to Modern Inorganic

Chemistry
R. D. Madan Modern Inorganic Chemistry
B. S. Bahl & Arun Bahl Advanced Organic Chemistry
 Lesson Plan on Structure of Atom
Lecture 01, Dept. of ME, Course: CHEM 1113
Toshar Hossain
Structure of Atom
About 2500 year ago, in old Greece, Leucippus and his student, Democritus gave the idea
that “all matters are composed of very tiny particles which cannot be further subdivided”.
Democritus named these particles “Atoms” that means which can not be further cut. But
under the influence of Greek philosopher Aristotle opposed to this idea and people forgot it
for about two thousand years. According to Aristotle, “matter is continuous, it can be
subdivided infinity.” But the atom theory became gradually popular among the scientists in
sixteenth and seventeenth centuries. At last a British school teacher, John Dalton re-
established the concept of atom as a scientific theory in 1803 and he is regarded as the
father of atomic theory.
 Dalton’s Atomic Theory
The English chemist John Dalton suggested that all matter is made up of atoms, which were
indivisible and indestructible. According to the postulates proposed by Dalton, the atomic
structure comprised atoms, the smallest particle responsible for the chemical reactions to occur.
Postulates of Dalton’s Atomic Theory
• All matter is made up of tiny, indivisible particles called atoms.
• All atoms of a specific element are identical in mass, size, and other properties. However,
atoms of different element exhibit different properties and vary in mass and size.
• Atoms can neither be created nor destroyed. Furthermore, atoms cannot be divided into
smaller particles.
• Atoms of different elements can combine with each other in fixed whole-number ratios in
order to form compounds.
• Atoms can be rearranged, combined, or separated in chemical reactions.
Dalton’s atomic theory successfully explained the Laws of chemical reactions, namely, the
Law of conservation of mass, Law of constant proportion, Law of multiple proportions
and Law of reciprocal proportions.
Limitations of Dalton’s Atomic Theory
• It does not account for subatomic particles: Dalton’s atomic theory stated that
atoms were indivisible. However, the discovery of subatomic particles (such as
protons, electrons, and neutrons) disproved this postulate.
• It does not account for isotopes: As per Dalton’s atomic theory, all atoms of an
element have identical masses and densities. However, different isotopes of
elements have different atomic masses (Example: hydrogen, deuterium, and
tritium).
• It does not account for isobars: This theory states that the masses of the atoms of
two different elements must differ. However, it is possible for two different
elements to share the same mass number. Such atoms are called isobars (Example:
40 40
18 Ar and 20Ca).
 Thomson Atomic Model
The English chemist Sir Joseph John Thomson put forth his model describing the
atomic structure in the early 1900s. He was later awarded the Nobel prize for the
discovery of “electrons”. His work is based on an experiment called cathode ray
experiment.
Cathode Ray Experiment
It has a tube made of glass which has two openings, one for the vacuum pump and the
other for the inlet through which a gas is pumped in. The role of the vacuum pump is
to maintain “partial vacuum” inside the glass chamber. A high voltage power supply is
connected using electrodes i.e. cathode and Anode is fitted inside the glass tube.
Observations:
▪ When a high voltage power supply is switched on, there were rays emerging from the
cathode towards the anode. This was confirmed by the ‘Fluorescent spots’ on the ZnS
screen used. These rays were called “Cathode Rays”.
▪ When an external electric field is applied, the cathode rays are attracted by the positive
charge, but in the absence of electric field, they travel in a straight line.
▪ When an external magnetic field is applied, the cathode rays are attracted by the north
pole of magnet.
▪ When rotor Blades are placed in the path of the cathode rays, they seem to rotate. This
proves that the cathode rays are made up of particles of a certain mass, so that they have
some energy.

Properties of Cathode Ray

i. They travel in straight line iii. They are negatively charged
ii. They posses some kinetic energy iv. They are affected by magnetic field
Conclusions:
▪ With all this evidence, Thompson concluded that cathode rays are made of negatively
charged particles called “electrons”.
▪ On applying the electric and magnetic field upon the cathode rays (electrons), Thomson
found the charge to mass ratio (e/m) of electrons. (e/m) for electron: 17588 × 1011 e/kg.
From this ratio, the charge of the electron was found by Millikan through oil drop
experiment. [Charge of e – = 1.6 × 10-16 C and Mass of e – = 9.1093 × 10- 31 kg]

Postulates of Thomson’s Atomic Model

➢Based on conclusions from his cathode ray experiment, Thomson described the atomic
structure as a positively charged sphere into which negatively charged electrons were
dispersed.
➢It is commonly referred to as the “plum pudding model” because it can be visualized as
a plum pudding dish where the pudding describes the positively charged atom and the
plum pieces describe the electrons.
➢Thomson’s atomic structure described atoms as electrically neutral, i.e. the positive and
the negative charges were of equal magnitude.
Limitations of Thomson’s Atomic Structure
Thomson’s atomic model does not clearly explain the stability of an atom. Also,
further discoveries of other subatomic particles, couldn’t be placed inside his atomic
model.
❖Later, The anode ray experiment also known as the canal ray experiment was
performed by German physicist Eugen Goldstein, and discover a type of ray with
the opposite properties of cathode ray and named as canals ray. Which is now
known as proton. More later, sir James Chadwick discovered the another
subatomic particle neutron.
What is Atomic Structure?
❑ The atomic structure of an element refers to the constitution of its nucleus and the
arrangement of the electrons around it. Primarily, the atomic structure of matter is
made up of protons, electrons and neutrons.
❑The protons and neutrons make up the nucleus of the atom, which is surrounded
by the electrons belonging to the atom. The atomic number of an element
describes the total number of protons in its nucleus.
❑Neutral atoms have equal numbers of protons and electrons. However, atoms may
gain or lose electrons in order to increase their stability and the resulting charged
entity is called an ion.
❑Atoms of different elements have different atomic structures because they contain
different numbers of protons and electrons. This is the reason for the unique
characteristics of different elements.
❑Atomic structure refers to the structure of atom comprising a nucleus (center) in
which the protons (positively charged) and neutrons (neutral) are present. The
negatively charged particles called electrons revolve around the center of the
nucleus. The history of atomic structure and quantum mechanics dates back to the
times of Democritus, the man who first proposed that matter is composed of
atoms.
 Fundamental Particles
The tiny particles that make up an atom are known as fundamental particles. It can
be classified into three types like-
1. Permanent fundamental particles, e.g., protons, electrons and neutrons.
2. Temporary fundamental particles, e.g., neutrino, antineutrino, positron, pion,
muon, boson, meson etc.
3. Composite fundamental particles, e.g., deuteron, alpha particle.

Characteristics of permanent fundamental particles

Name Symbol Actual Charge Relative Charge Actual Mass Relative Mass

Electron 𝑒− -1.6×10−19 C -1 9.11×10−31 Kg 0

Proton P or 𝐻 + 1.6×10−19 C 1 1.673×10−27 Kg 1

Neutron n 0 0 1.675×10−27 Kg 1
Isotope
Different atoms of same element which have same number of proton (P) , but due to having
different number of neutron (n), mass number become different, these are called isotope
with each other. Example: 11H, 21H, 31H
Isobar
Different atoms of different elements which have different number of proton (P) and
neutron (n) , but mass numbers are equal/same, these are called isobar with each other.
Example: 40 40
18Ar and 20Ca
Isotone
Different atoms of different elements which have same number of neutron (n), but due to
having different number of proton (P), mass number become different, these are called
isotone with each other. Example: 157N and 168O
Iso-electronic
Those species which have same number of electrons(𝑒 − )are called iso-electronic with each
other. Example: F − , Ne, Na+ , Mg 2+
 Lesson Plan on Structure of Atom
Lecture 02, Dept. of ME, Course: CHEM 1113
Toshar Hossain
Nuclear Charge( Z)
The nuclear charge is the total charge of all the Protons in the nucleus. It has the
same value as the atomic number.
Effective Nuclear Charge
Effective nuclear charge is the charge felt by the valence electrons after we have
taken into account the number of shielding electrons that surround the nucleus. The
effective nuclear charge (Z effective or Zeff) is defined as the net positive charge
pulling outermost electrons towards the nucleus. The stronger the pull on the
outermost electrons (valence electrons) towards the nucleus, the higher the effective
nuclear charge, Zeff = Z- S ; Where S represents shielding effect.
Atomic Number
The total number of unit positive charges on the nucleus is called the atomic number
of the element.
 Rutherford’s atomic model – The nuclear model
In 1911, Rutherford perform his famous gold foil experiment which is also known
as Rutherford’s alpha(α) particle scattering experiment. With the help of this
experiment Rutherford’s describe some important information about atoms.
Alpha(α) particle
alpha(α) particle is a helium nucleus which have two units of positive charge and its
mass number is equal to 4.
He - 2e− → He2+ (alpha(α) particle )
Materials used of Rutherford’s experiment
i. Radioactive Radium(Ra) as a source of alpha(α) particle.
ii. Thin gold foil( 0.00004cm Thickness)
iii. A screen coated with ZnS
Experiment
In his gold foil experiment, Rutherford bombarded a beam of alpha particles on an
ultrathin gold foil and then detected the scattered alpha particles in zinc sulfide
(ZnS) screen. This experiment is known as Rutherford’s alpha(α) particle
scattering experiment.
Observations
• Most of the particles (about 99%) pass through the foil without any deflection.
• Some of the alpha particles deflect at small angle.
• Very few even bounce back (1 in 20,000).
Conclusions
Based on his observations, Rutherford proposed the following structural features of
an atom:
➢Most of the atoms mass and its entire positive charge are confined in a small core,
called nucleus. The positively charged particle is called proton.
➢Most of the volume of an atom is empty space.
➢The number of negatively charged electrons dispersed outside the nucleus is same
as number of positively charge in the nucleus. It explains the overall electrical
neutrality of an atom.
Postulates of Rutherford’s Atomic Model
▪ Atom contains a massive (heavy) and positively
charged part at its center. This central part of
atom is called nucleus. The size of nucleus is
very small as compared to that of hole atom.
Thus the atom contains a lot of empty space
round the nucleus. The entire mass of the atom
resides in its nucleus.
▪ Atoms are electrically neutral. Therefore, there are an equal number of negative
charges revolving outside the nucleus as there are positive charges in the nucleus.
▪ Like planets revolving around the sun in the solar system, electrons revolve around the
nucleus in atoms. The centripetal force due to electrostatic interaction between the
positively charged nucleus and the negatively charged electrons and centrifugal force
due to the rotating electrons are equal and opposite to each other, that’s why they are
counter-balanced.
Limitations of Rutherford’s atomic model
➢The model has been compared with the solar system. The rotating electrons are
negatively charged and repel each other while the rotating planets are neutral and
have force of gravitation acting between them. On the other hand, the force
between nucleus and electrons is electrostatic. So, comparison between
gravitational force and electrostatic force is not correct.
➢ According to Maxwell’s electromagnetic theory, any
charged particle while revolving will emit radiation
and lose energy. Thus, rotating electrons round the
nucleus will lose energy and its orbit will become
smaller and smaller and it will ultimately fall into
the nucleus following a spiral path. But it does not
occur practically.
➢This model cannot explain atomic spectra.
➢Rutherford did not give any idea about the shape and size of the orbits of electron
in atom.
➢There was no explanation about the rotation of many electrons in an orbit.

❑ Due to the close resembles of Rutherford’s Atomic Model with solar system this
model is said to be ‘Solar system atom model’. Also due to the discovery of
nucleus this model is said to be ‘Nuclear model’.
 Bohr’s atomic model
In 1913, Neil’s Bohr proposed his famous atom model, which not only described the
structure of atom but also gave an explanation about the origin of atomic spectra. The
postulates of Bohr’s atom model can be divided into the following important parts as
follows:
1. Concept of stationary orbit or energy level or shell: Electrons travel around the
nucleus in specific permitted circular orbits. While in these specific orbits, an
electron does not radiate (or lose) energy. These circular paths are known as
stationary orbits or energy levels of electrons. An electron can’t emits or absorb
energy while in a specific orbit. These orbits are said to be stationary orbits or orbit
or energy level or shell.
 Lesson Plan on Structure of Atom
Lecture 03, Dept. of ME, Course: CHEM 1113
Toshar Hossain
2. Concept of angular momentum of electrons: In a certain orbit, the angular
momentum (mvr) of a moving electron around the nucleus is an integral multiple of
h
2π
3. Concept of energy absorption or emission: When an electron is excited from a
lower energy state to a higher energy state, it absorbs energy. On the other hand
when it comes back from a higher energy level to a lower energy level, it emits
energy. The absorption or emission of energy takes place in the form of quanta or
photon and is equal to hυ. (The absorption or emission of energy takes place not as a
continuous waves but as small packets or bundles or separate units of waves each of
which is called a quantum (plural quanta) or photon). Energy absorbed or emitted by
electrons as follows-
ℎ𝑐
∆E= 𝐸2 - 𝐸1 = hυ=
𝜆
Success of Bohr’s Atomic Model (Got Nobel prize in 1922)
i. Able to explain the stability of atoms.
ii. Became able to explain hydrogen Spectrum.
iii. Became able to calculate the wave-length.
iv. Became able to calculate the radius of orbit.
Limitations of Bohr’s atomic model
▪ Bohr’s theory has successfully explained the origin of spectrum of hydrogen atom
and of hydrogen-like ions (e.g., He+ , Li2+ Be3+ etc.) which are one-electron
systems, but it is not able to explain the origin of spectrum of multi-electron
systems.
▪ Bohr’s theory has successfully explained the origin of hydrogen spectrum, but
when the hydrogen spectrum is observed by means of spectroscope of high
resolving power, it is found that, the individual spectral lines are not really single
but consist of several very fine lines lying together. These spectral lines are said to
be fine structure. This fine structure of spectral lines in hydrogen spectrum can’t
be explained by Bohr’s theory.
▪ Atomic model is not flat as suggested by Bohr, but has a three-dimensional
existence.
▪ Bohr’s theory can’t explain Zeeman and Stark effect.
▪ Bohr’s theory can’t explain dual nature of electrons and Heisenberg’s Uncertainty
principle

Comparison between Rutherford’s and Bohr’s Atomic Model

➢The basis of Rutherford’s Atomic Model is Max-Well’s Electromagnetic theory
whereas The basis Bohr’s Atomic Model is Max-Plank’s Quantum theory.
➢Rutherford’s Atomic Model is unable to explain Emission/absorption spectra but
Bohr’s Atomic Model is able.
➢Rutherford’s Atomic Model is unable to explain about shape and size of orbitals
but Bohr’s Atomic Model is able to explain it.
➢Rutherford’s Atomic Model can’t explain the stability of atom but Bohr’s Atomic
Model can able to explain it clearly.
➢ Rutherford’s couldn’t give any idea about angular momentum but according to
Bohr’s Atomic Model, In a certain orbit, the angular momentum (mvr) of a
h 𝑛h
moving electron around the nucleus is an integral multiple of i.e., mvr=
2π 2π
Bohr’s Explanation of Hydrogen Spectrum
The solitary electron in hydrogen atom at ordinary temperature resides in the first
orbit (n = 1) and is in the lowest energy state (ground state). When energy is
supplied to hydrogen gas in the discharge tube, the electron moves to higher energy
levels viz., 2, 3, 4, 5, 6, 7, etc., depending on the quantity of energy absorbed. From
these high energy levels, the electron returns by jumps to one or other lower energy
level. In doing so the electron emits the excess energy as a photon.
This gives an excellent explanation of the various spectral series of hydrogen.
Lyman series is obtained when the electron returns to the ground state i.e., n = 1
from higher energy levels (n2 = 2, 3, 4, 5, etc.). Similarly, Balmer, Paschen, Brackett
and Pfund series are produced when the electron returns to the second, third, fourth
and fifth energy levels respectively.
Wave number of various hydrogen spectrum can be calculate with the help of
Rydberg's equation as follows-
1 1
ῡ = 𝑅𝐻 ( - )
𝑛12 𝑛22
𝑅𝐻 = Rydberg’s constant
=1.09678×107 𝑚−1
= 1.09678×105 𝑐𝑚−1
= 1.09678×10−2 𝑛𝑚−1

1 𝑐 ℎ𝑐
ῡ= υ= ∆E= hυ=
𝛌 𝜆 𝜆
Problem solving on Hydrogen spectra
Problem solving
1. Calculate the wavelength, frequency and energy respect to the 3 1 emission
spectra in hydrogen spectrum.
2. Calculate the wavelength, frequency and energy for 4th line of Balmer series in
hydrogen spectrum.
3. Calculate the wavelength, frequency and energy for 𝐻β emission of Paschen
series in hydrogen spectrum.
4. Determine the maximum wavelength, frequency and energy observe in Bracket
series.
5. An excited electron of hydrogen atom is fall down from 7th orbit to ground state.
What region of electromagnetic spectrum was obtained? Explain
mathematically.
6. An excited electron of hydrogen atom is return back to the normal state from
infinity. Find out the amount of energy emission for responsible transition.
 Lesson Plan on Structure of Atom
Lecture 04, Dept. of ME, Course: CHEM 1113
Toshar Hossain
Quantum Numbers
The numbers that provide information about the size, shape, three-dimensional
arrangement of orbit, and direction of spin of an electron are called quantum
numbers.
Classifications
Quantum numbers can be classified into four types-
1. Principle quantum number (n)
2. Azimuthal/ Subsidiary quantum number (l)
3. Magnetic quantum number (m)
4. Spin quantum number (𝑚𝑠 )
Principle quantum number (n)
The quantum numbers that provide information about the size of an orbit are said to
be principle quantum number. This quantum number denotes the principal shell to
which the electron belongs. This is also referred to as major energy level or shell. It
represents the average size of the electron cloud i.e., the average distance of the
electron from the nucleus. The principal quantum number ‘n’ can have non-zero,
positive, integral values n = 1, 2, 3... increasing by integral numbers to infinity. The
letters K, L, M, N, O, P and Q are also used to designate the energy levels or shells
or orbit of electrons with a n value of 1, 2, 3, 4, 5, 6, 7 respectively.
Azimuthal/ Subsidiary quantum number (l)
The quantum numbers that provide information about the shape of an orbit are said
to be azimuthal/ subsidiary quantum number. It defines the spatial distribution of the
electron cloud about the nucleus and describes the angular momentum of the
electron. In other words, the quantum number l defines the shape of the orbital
occupied by the electron and the angular momentum of the electron. For any given
value of the principal quantum number n, the azimuthal quantum number l may have
all integral values from 0 to n – 1, each of which refers to an Sub-shell.

Azimuthal quantum number(l) 0 1 2 3

Latter designation s p d f
Maximum capacity of 2 6 10 14
electrons{2(2l+1)}
Azimuthal quantum number and sub-shell correspond to principle
quantum number-

Magnetic quantum number (𝑚)

The quantum numbers that provide information about the three-dimensional
arrangement of orbit are said to be magnetic quantum number.
This is also called Orientation Quantum Number because it gives
The orientation or distribution of the electron cloud. For any values of l,
m should be (2l+1) numbers of value. For each value of the azimuthal
quantum number ‘l’, the magnetic quantum number m, may assume all
the integral values between - 1 to + l through zero i.e., for l=1, m should
be – l.0,+1 each of which refers to an orbital. Different orbitals of
equivalent energy are called degenerate orbitals and are grouped
together.
m =-Values for respective orbital
Orbitals 𝑷𝒙 𝑷𝒚 𝑷𝒛 𝒅𝒙𝒚 𝒅𝒚𝒛 𝒅𝒛𝒙 𝒅𝒙𝟐 −𝒚𝟐 𝒅𝒛𝟐
m- Value 0 +1 -1 -2 -1 +1 +2 0

𝒅 𝒛𝟐 𝒅𝒙𝟐 −𝒚𝟐
Spin quantum number (𝑚𝑠 )
The quantum numbers that provide information about the direction of spin of an
electron about its own axis are said to be spin quantum number. Since an electron can
spin clockwise or anticlockwise (in two opposite directions), there are two possible
1 1
values of 𝑚𝑠 that are equal and opposite. It has two allowed values, + and - .
2 2
1 1
+ value represents the anticlockwise whereas - value represents the clockwise
2 2
direction.
 Lesson Plan on Structure of Atom
Lecture 05, Dept. of ME, Course: CHEM 1113
Toshar Hossain
Determination of orbitals and electron number in different shell depending on n, l
and m values:
Difference between orbit and orbital
Orbit Orbital
A specific permitted circular path in A region around the nucleus at which
which electrons are revolving round the probability of findings electron is
the nucleus is known as orbit. maximum (90%-95%) is known as
orbital.
Maximum capacity of electrons is 2𝑛2 An orbital occupy only two electrons.

Letter designation of orbit is K, L, M, Letter designation of orbital is 𝑝𝑥 , 𝑝𝑦 ,

N etc. 𝑝𝑧 , 𝑑𝑥𝑦 , 𝑑𝑦𝑧 etc.
Orbit is circular only. Orbital should be spherical or
ellipsoidal
With the increase of principle quantum Each magnetic quantum number
number size of orbit is also increase. represent a different orbital.
Electronic configurations
The distribution of electrons in various shells, sub-shells and orbitals of an atom is
called it’s electronic configuration.
Principles for electronic configuration
There are three principles for electron configuration. Which are-
1. Aufbau Principle
2. Hund’s rule of maximum multiplicity
3. Pauli’s Exclusion Principle

Aufbau Principle
Aufbau is a German word which means build up or construction. It is for this reason
that the principle is also often called building up principle or construction principle.
It is pronounced as of bow. This principle gives us a sequence in which various
orbitals are filled with electrons. This principle states as follows: The orbitals are
filled up with electrons in the increasing order of their energy.
The principle can also be restated in any of the following forms :
i. The orbitals of minimum energy are filled up first with electrons and then the
orbitals of higher energy start to fill.
ii. The relative order of energy of different orbitals (or the sequence in which
various orbitals are filled up with electrons) can be determined with the help of
(n+l) value for a given orbital (n = principal quantum number, l=azimuthal
quantum number). This rule is called (n + 1) rule. According to this rule: The
orbital having the lowest value of (n +l) has the lowest energy and hence is
filled up first with electrons. For example , in case of 3d orbital n+l=5 and , for
4s orbital n+l=4. therefore, 4s is lower energy orbital and occupy first. When
two or more orbitals have the same value of (n +l), the orbital with lower value
of n is lower in energy and hence is filled up first with electrons. Thus the order
of energies of 3d, 4p and 5s orbitals for all of which (n+l)=5 is as:
3d(n=3)<4p(n=4)<5s(n=5), since n for these orbitals is 3,4 and 5 respectively.
Thus orbitals will be filled up with electrons in the following sequence:
Hund’s rule of maximum multiplicity
This rule is based on the fact that electrons, being of the same charge, repel each
other and hence try to keep farther apart from each other as much as possible. This
they do by entering the degenerate orbitals as far as possible. Their entering the
orbitals in this manner minimizes the inter-electronic repulsion energy of the system
and hence we get a stable system. Thus we can also call this rule as a rule of
minimum energy. This rule can be stated in any of the following forms:
i. When electrons enter a set of orbitals of a given sub-shell, electrons will pair up
only when all the available orbitals have had at least one electron each.
ii. The orbitals of a given sub-shell are first filled singly and then the pairing of
electrons in each orbital begins.
iii. When several orbitals of equal energy (degenerate orbitals) are available,
electrons prefer to occupy separate orbitals, rather than getting paired in the
same orbital. Such electrons tend to have the same spins. This principle means
that pairing of electrons begins with the introduction of 2rld electron in s-
orbital, the 4th electron in p-orbitals, 6th electron in d-orbitals and 8th electron
inf-orbitals.
Illustration of Hund’s rule
Pauli’s Exclusion Principle
This rule’s state that, In the same orbital of an atom, two electrons can have three
quantum numbers identical at the most, but the fourth quantum number, namely spin
quantum number (s), will definitely be different for both the electron, i.e., for one
electrons will be +1/2 while for the other electron it will be-1/2. In other words, this
means that two electrons residing in the same orbital of an atom have opposite spins,
since this state with opposite spins(↑↓)gives lower energy to the system, while the
state with parallel spins (↑↑)gives higher energy to the system. According to
thermodynamics, a system with lower energy has greater stability.
In other words, An orbital like s, Px ,Py ,dxy ,dyz etc. can have at the most two
electrons and these two electrons must have opposite spins i.e. one electron should
have the value of s equal to +1/2 and the other equal to-1/2,so that both the electrons
residing in the same orbital may have different sets of four quantum numbers.
Illustration of Pauli’s exclusion principle