Course Title: Chemistry I
Fundamental of Chemistry
MD. SOHANUR RAHMAN
[Link]. (Organic Chemistry) 1st Class First, BUET
Pursuing [Link]. (Organic Chemistry), BUET
Lecturer (Chemistry)
Department of Computer Science & Engineering
Faculty of Science & Engineering
Northern University of Business and Technology, Khulna
Chapter-1
Atomic Structure
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.
Structure of atom
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.
Subatomic Particles
Protons
• Protons are positively charged subatomic particles. The charge of a proton is 1e, which
corresponds to approximately 1.602 × 10-19
• The mass of a proton is approximately 1.672 × 10-24
• Protons are over 1800 times heavier than electrons.
• The total number of protons in the atoms of an element is always equal to the atomic
number of the element.
Neutrons
• The mass of a neutron is almost the same as that of a proton, i.e., 1.674×10-24
• Neutrons are electrically neutral particles and carry no charge.
• Different isotopes of an element have the same number of protons but vary in the number
of neutrons present in their respective nuclei.
Electrons
• The charge of an electron is -1e, which approximates to -1.602 × 10-19
• The mass of an electron is approximately 9.1 × 10-31.
• Due to the relatively negligible mass of electrons, they are ignored when calculating the
mass of an atom.
Atomic Models
In the 18th and 19th centuries, many scientists attempted to explain the structure of the atom with
the help of atomic models. Each of these models had its own merits and demerits and was pivotal
to the development of the modern atomic model. The most notable contributions to the field were
by scientists such as John Dalton, J.J. Thomson, Ernest Rutherford, and Niels Bohr. Their ideas
on the structure of the atom are discussed in this subsection.
Dalton’s Atomic Theory
The English chemist John Dalton suggested that all matter is made up of atoms, which were
indivisible and indestructible. He also stated that all the atoms of an element were exactly the same,
but the atoms of different elements differ in size and mass.
Chemical reactions, according to Dalton’s atomic theory, involve a rearrangement of atoms to
form products. According to the postulates proposed by Dalton, the atomic structure comprises
atoms, the smallest particle responsible for the chemical reactions to occur.
The following are the postulates of his theory:
• Every matter is made up of atoms.
• Atoms are indivisible.
• Specific elements have only one type of atom in them.
• Each atom has its own constant mass that varies from element to element.
• Atoms undergo rearrangement during a chemical reaction.
• Atoms can neither be created nor destroyed but can be transformed from one form to
another.
Dalton’s atomic theory successfully explained the Laws of chemical reactions, namely, the Law
of conservation of mass, the Law of constant properties, the Law of multiple proportions and the
Law of reciprocal proportions.
Demerits of Dalton’s Atomic Theory
• The theory was unable to explain the existence of isotopes.
• Nothing about the structure of the atom was appropriately explained.
• Later, scientists discovered particles inside the atom that proved the atoms are divisible.
The discovery of particles inside atoms led to a better understanding of chemical species; these
particles inside the atoms are called subatomic particles. The discovery of various subatomic
particles is as follows:
Thomson Atomic Model
Thomson's Atomic Model and Its Limitations
In order to understand the various chemical reactions that occur around us and the parameters
governing these reactions, we need an understanding of the elements and compounds taking part
in these reactions. The early developments in science revealed that matter is made up of atoms
which in turn are composed of elementary particles known as electrons, protons and neutrons. In
order to have a better understanding of the transformations of matter from one form to the other,
scientists needed a defined structure for an atom and its interaction with other atoms. J.J. Thomson,
an English scientist, proposed the famous Thomson atomic model in the year 1898 just after the
discovery of electrons.
Plum Pudding Atomic Theory
Thomson proposed that the shape of an atom resembles that of a sphere having a radius of the
order of 10-10 m. The positively charged particles are uniformly distributed with electrons arranged
in such a manner that the atom is electrostatically stable. Thomson’s atomic model was also called
the plum pudding model or the watermelon model. The embedded electrons resembled the seed of
a watermelon while the watermelon’s red mass represented the positive charge distribution. The
plum pudding atomic theory assumed that the mass of an atom is uniformly distributed all over the
atom.
Limitations of Thomson’s Atomic Model
Thomson’s atomic model explained the overall neutrality of an atom. Its assumption that the total
mass of an atom is uniformly distributed all over the atom was inconsistent with some experimental
results. Rutherford’s gold foil experiment of scattering α-particles revealed that most of the space
in an atom is empty, contradicting Thomson’s atomic model. Thus, it was found that the plum
pudding atomic model was insufficient to explain the structure of an atom.
The limitations of Thomson’s atomic model triggered further research for establishing the structure
of an atom. The plum pudding atomic model lacked experimental evidence and hence Rutherford
conducted many experiments in order to determine the structure of an atom.
Rutherford Atomic Model
Rutherford Atomic Model – The plum pudding model 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
explained the atomic structure of elements and proposed Rutherford’s Atomic Model.
Table of Contents
• Rutherford’s Alpha Scattering Experiment
• Observations of Rutherford’s Alpha Scattering Experiment
• Rutherford Atomic Model
• Limitations of the Rutherford Atomic Model
Rutherford’s Alpha Scattering Experiment
Rutherford 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 Atomic Model
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 the
sheet 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
180o 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 positive charge and most of the mass of an atom is concentrated in an extremely small
volume. He called this region of the atom as a nucleus.
2. Rutherford’s 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.
• Rutherford proposed that the electrons revolve around the nucleus in fixed paths called
orbits. According to Maxwell, accelerated charged particles emit electromagnetic
radiation, 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 into the nucleus in less than 10-8 seconds. So, the Rutherford model was not in
accordance with Maxwell’s theory and could not explain the stability of an atom.
• 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.
• Although the early atomic models were inaccurate and failed to explain certain
experimental results, they formed the base for future developments in the world of
quantum mechanics.
Bohr’s Model of an Atom
The Bohr model of the atom was proposed by Neil Bohr in 1915. It came into existence with the
modification of Rutherford’s model of an atom. Rutherford’s model introduced the nuclear
model of an atom, in which he explained that a nucleus (positively charged) is surrounded by
negatively charged electrons.
Introduction to the Bohr Model
Bohr's theory modified the atomic structure model by explaining that electrons move in fixed
orbitals (shells) and not anywhere in between and he also explained that each orbit (shell) has a
fixed energy. Rutherford explained the nucleus of an atom and Bohr modified that model into
electrons and their energy levels.
Bohr’s Model of an Atom
Bohr’s model consists of a small nucleus (positively charged) surrounded by negative electrons
moving around the nucleus in orbits. Bohr found that an electron located away from the nucleus
has more energy, and the electron which is closer to nucleus has less energy
Postulates of Bohr’s Model of an Atom
• In an atom, electrons (negatively charged) revolve around the positively charged nucleus
in a definite circular path called orbits or shells.
• Each orbit or shell has a fixed energy and these circular orbits are known as orbital shells.
• The energy levels are represented by an integer (n=1, 2, 3…) known as the quantum
number. This range of quantum number starts from nucleus side with n=1 having the
lowest energy level. The orbits n=1, 2, 3, 4… are assigned as K, L, M, N…. shells and
when an electron attain the lowest energy level, it is said to be in the ground state.
• The electrons in an atom move from a lower energy level to a higher energy level by
gaining the required energy and an electron moves from a higher energy level to lower
energy level by losing energy.
Limitations of Bohr’s Model of an Atom
• Bohr’s model of an atom failed to explain the Zeeman Effect (effect of magnetic field on
the spectra of atoms).
• It also failed to explain the Stark effect (effect of electric field on the spectra of atoms).
• It violates the Heisenberg Uncertainty Principle.
• It could not explain the spectra obtained from larger atoms.
Heisenberg’s Uncertainty Principle
Heisenberg’s uncertainty principle states that for particles exhibiting both particle and wave
nature, it will not be possible to accurately determine both the position and velocity at the same
time. The principle is named after German physicist Werner Heisenberg, who proposed the
uncertainty principle in the year 1927. This principle was formulated when Heisenberg was trying
to build an intuitive model of quantum physics. He discovered that there were certain fundamental
factors that limited our actions in knowing certain quantities.
This principle basically highlights that simultaneous measurement of position and the velocity or
momentum of microscopic matter waves will have an error such that the product of the error in
measurement of position and momentum is equal or more than an integral multiple of a constant.
Origin of the Uncertainty Principle
One of the crucial points for the genesis of the uncertainty principle is solely due to the dual nature
of a wave-particle. Every particle is said to have a wave nature, and the probability of finding
particles is maximum, where the waveforms are the greatest. If the particle has greater undulation,
the wavelength becomes more indistinct or vague. However, we are able to determine the
momentum of the particle. From what we have learnt so far, we can say that the particles that have
definite positions will have no fixed velocity. On the other hand, a particle with a well-defined
wavelength will show a definitive or precise velocity. All in all, if we get an accurate reading of
one quantity, it will only lead to large uncertainty in the measurement of the other.
Heisenberg Uncertainty Principle: Formula and Application
If ∆x is the error in position measurement and ∆p is the error in the measurement of momentum,
then
Since momentum, p = mv, Heisenberg’s uncertainty principle formula can be alternatively written
as,
Where ∆V is the error in the measurement of velocity, and assuming mass remains constant during
the experiment,
.
Accurate measurement of position or momentum automatically indicates larger uncertainty (error)
in the measurement of the other quantity.
Applying the Heisenberg principle to an electron in an orbit of an atom, with h = 6.626 ×10-34Js
and m= 9.11 ×10-31Kg,
If the position of the electron is measured accurately to its size (10-10m), then the error in the
measurement of its velocity will be equal to or larger than 106m or 1000 km.
Heisenberg’s principle applies to only dual-natured microscopic particles and not to macroscopic
particles whose wave nature is minimal.
Explaining Heisenberg Uncertainty Principle with an Example
Electromagnetic radiations and microscopic matter waves exhibit a dual nature of
mass/momentum and wave character. The position and velocity/momentum of macroscopic matter
waves can be determined accurately and simultaneously. For example, the location and speed of a
moving car can be determined simultaneously with minimum error. But, in microscopic particles,
it will not be possible to fix the position and measure the velocity/momentum of the particle
simultaneously.
An electron in an atom has a mass of 9.91 × 10-31 kg. Naked eyes cannot see such small particles.
A powerful light may collide with the electron and illuminate it. Illumination helps in identifying
and measuring the position of the electron. The collision of the powerful light source, while
helping in identification, increases the momentum of the electron and makes it move away from
the initial position. Thus, when fixing the position, the velocity/momentum of the particle would
have changed from the original value. Hence, when the position is exact, the error occurs in
measuring velocity or momentum. In the same way, the measurement of momentum, accurately,
will change the position.
Hence, at any point in time, either position or momentum can only be measured accurately.
Simultaneous measurement of both of them will have an error in both position and momentum.
Heisenberg quantified the error in the measurement of both position and momentum
simultaneously.
Quantum Numbers
Quantum numbers in Chemistry, are the sets of numbers that describe an electron’s trajectory and
movement within an atom. When the quantum numbers of all the electrons in a given atom are
added together, they must satisfy the Schrodinger equation. Quantum numbers are the set of
numbers used to describe the position and energy of an electron in an atom. There are four types
of quantum numbers: principal, azimuthal, magnetic, and spin. Quantum numbers represent the
values of a quantum system’s conserved quantities.
Let’s learn about all the quantum numbers in detail in this article.
What are Quantum Numbers?
Quantum numbers are the set of constant values in the quantum approach. Quantum Numbers
or Electronic quantum numbers describe an electron with numerical values that provide
solutions to the Schrodinger wave equation for hydrogen atoms these numbers can define the
position, energy and orientation of an electron in an atom through the set of numbers.
According to the Pauli exclusion principle, no two electrons in an atom may have the same set
of quantum numbers, A half-integer or integer value is used to characterize each quantum number.
The principal, azimuthal and magnetic quantum numbers are respectively related to the size, shape,
and orientation of the atom.
Four quantum numbers can be used to fully describe all of the properties of a given electron in an
atom; these are:
1. Principal quantum number
2. Orbital angular momentum quantum number (or Azimuthal quantum number).
3. Magnetic quantum number
4. The electron spin quantum number
Types of Quantum Numbers
The four-quantum number totally defines an electron in an atom or provides complete knowledge
of an electron in an atom. The four quantum numbers are:
• Principal Quantum Number (n)
• Azimuthal Quantum Number (l)
• Magnetic Quantum Number (ml)
• Electron Spin Quantum Number (s)
Principal Quantum Number (n)
The symbol ‘n’ represents the principal quantum numbers. They denote the atom’s primary
electron shell. Because it describes the most likely distance between the nucleus and the electrons,
a larger value of the principal quantum number implies a greater distance between the electron and
the nucleus (which, in turn, implies a greater atomic size).
• The principal quantum number’s value can be any integer with a positive value equal
to or greater than one. The value n=1 denotes an atom’s innermost electron shell, which
corresponds to an electron’s lowest energy state (or ground state).
• As a result, the principal quantum number, n, cannot have a negative value or be equal
to zero because an atom cannot have a negative value or no value for a principal shell.
• When an electron is infused with energy (excited state), the electron jumps from one
principal shell to a higher shell, causing the value of n to increase.
• Similarly, as electrons lose energy, they return to lower shells, lowering the value of n.
Absorption refers to the increase in the value of n for an electron, emphasizing the
photons or energy absorbed by the electron.
• Similarly, a decrease in the value of n for an electron is referred to as emission, and this
is where the electrons emit their energy.
Azimuthal Quantum Number (l)
The azimuthal quantum number (or orbital angular momentum) describes the shape of an orbital.
It is represented by the letter ‘l,’ and its value equals the total number of angular nodes in the
orbital.
• A value of the azimuthal quantum number can denote either an s, p, d, or f subshell,
the shapes of which vary.
• This value is determined by (and limited by) the value of the principal quantum number,
i.e. the azimuthal quantum number ranges between 0 and (n-1).
• For example, if n = 3, the azimuthal quantum number can have three values: 0, 1, and
2.
• When l is set to zero, the resulting subshell is an ‘s’ subshell.
• When l=1 and l=2, the resulting subshells are ‘p’ and ‘d’ subshells, respectively
(respectively).
• As a result, when n=3, the three subshells that can exist are 3s, 3p, and 3d. In another
case where n = 5, the possible values of l are 0, 1, 2, 3, and 4. If l = 3, the atom contains
three angular nodes.
Magnetic Quantum Number (ml)
The magnetic quantum number determines the total number of orbitals in a subshell as well as
their orientation. It is represented by the symbol ‘ml.’ This number represents the projection of the
orbital’s angular momentum along a given axis.
• The magnetic quantum number is determined by the azimuthal (or orbital angular
momentum) quantum number.
• For a given value of l, the value of ml falls between -l and +l. As a result, it is indirectly
dependent on the value of n.
• For example, if n = 4 and l = 3 in an atom, the magnetic quantum number can be -3, -
2, -1, 0, +1, +2, and +3. The total number of orbitals in a given subshell is determined
by the orbital’s ‘l’ value.
• It is calculated using the formula (2l + 1). The ‘3d’ subshell (n=3, l=2), for example,
has 5 orbitals (2*2 + 1). Each orbital can hold two electrons. As a result, the 3d subshell
can accommodate a total of 10 electrons.
Electron Spin Quantum Number (s)
The electron spin quantum number is independent of n, l, and ml values. The value of this number,
denoted by the symbol ms, indicates the direction in which the electron is spinning.
• The ms value indicates the direction in which the electron is spinning. The electron spin
quantum number can have values between +1/2 and -1/2.
• A positive value of ms denotes an upward spin on the electron, also known as spin up.
• If ms is negative, the electron in question is said to have a downward spin or spin down.
• The value of the electron spin quantum number determines whether or not the atom in
question can generate a magnetic field. The value of ms can be generalized to ±½.
Significance of Quantum Numbers
Quantum numbers are significant because they can be used to estimate an atom’s electron
configuration and where its electrons are most likely to be located. The atomic radius and
ionization energy of atoms, among other properties, is also determined by quantum numbers.
Each Quantum Number has its own significance:
• Principal Quantum Number (n) describes the electron levels of an atom.
• Azimuthal Quantum Number (l) represents the shape of the electron cloud.
• Magnetic Quantum Number (ml) explains the orientation of the electron cloud.
• Spin Quantum Number (s) tells the spin electrons can have.
Atomic Orbital
As we know that electrons behave like waves and the position of the electron inside the atom can
easily be defined with the help of the wave theory of quantum mechanics by solving the
Schrodinger wave equation at the specific energy level of an atom.
These wave functions that define the position of an electron inside an atom are called atomic
orbitals. These orbitals are the places that have the highest probability of finding the electron.
There are four types of orbitals inside an atom
• s – orbital
• p – orbital
• d – orbital
• f – orbital
Atomic orbitals are also defined as the physical space inside the atom where the probability of
finding the electron is highest.
Solved Examples on Quantum Numbers
Example 1: Find all four quantum numbers of the last electron of the Rubidium.
Solution:
Rubidium has the atomic number, Z = 37.
Electronic Configuration of Rubidium,
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s1
Valence last shell electron is 5s1
Therefore,
Principal Quantum Number, n = 5,
Azimuthal Quantum Number, l = 0,
Magnetic Quantum Number, ml = 0,
Spin Quantum Number, s = +1/2
Example 2: State the possible values of the magnetic quantum number for l = 2.
Solution:
Given that, the Azimuthal Quantum Number, l = 2
We know that,
ml = – l to + l
Therefore,
ml = -2 to +2
i.e.
m2 = -2, -1, 0, +1, +2
Example 3: Find all four quantum numbers of the last electron of the Sodium.
Solution:
Sodium has the atomic number, Z = 11.
Electronic Configuration of Rubidium,
1s2 2s2 2p6 3s1
Vlence shell last electron is 3s1
Therefore,
Principal Quantum Number, n = 3,
Azimuthal Quantum Number, l = 0,
Magnetic Quantum Number, ml = 0,
Spin Quantum Number, s = +1/2
Example 4: State the possible values of the magnetic quantum number for l = 3.
Solution:
Given that, the Azimuthal Quantum Number, l = 3
We know that,
for l = 3,
ml = – 3 to + 3
i.e.
m = -3, -2, -1, 0, +1, +2 +3
FAQs on Quantum Numbers
Question 1: Define Quantum Numbers.
Answer:
The set of numbers which are used to define the position and energy of the number of electrons in
an atom are called quantum numbers.
Question 2: How many quantum numbers are there?
Answer:
The four quantum numbers are,
• Principal Quantum Number (n)
• Azimuthal Quantum Number (l)
• Magnetic Quantum Number (ml)
• Electron Spin Quantum Number (s)
Question 3: Which quantum number specifies the shape of an orbital?
Answer:
Azimuthal Quantum Number (l) also called Angular quantum number defines the shape of the
orbital.
Question 4: Which quantum number determines the orientation of the orbital?
Answer:
Magnetic Quantum Number (ml) is used to represent the orientation of the orbital in the three-
dimensional space.
Question 5: How many quantum numbers are required to specify an orbital?
Answer:
Three quantum numbers are required to specify the orbital of an atom which are,
• Principal Quantum Number (n)
• Azimuthal Quantum Number (l)
• Magnetic Quantum Number (ml)
Question 6: Which quantum number determines the energy of the electron?
Answer:
The energy of the electron can easily be determined by using the principal quantum number(n) and
Azimuthal Quantum Number(l) of an electron.
Question 7: What is Quantum Energy?
Answer:
The energy of quantum particles (i.e., very small particles) is called quantum energy. One way to
measure quantum energy is using Photon which is the smallest unit to measure light energy and
energy of other electromagnetic waves.
Question 8: What is the spin of an electron?
Answer:
Electron spin is a quantum property of electrons. It is a shape with angular momentum. As a
teaching technique, instructors compare electron spin to the planet rotating on its own axis every
24 hours. Spin-up occurs when the electron spins clockwise on its axis; spin-down occurs when
the electron spins counterclockwise.
Electron Configurations
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.
However, the standard notation often yields lengthy electron configurations (especially for
elements having a relatively large atomic number). In such cases, an abbreviated or condensed
notation may be used instead of the standard notation. In the abbreviated notation, the sequence
of completely filled subshells that correspond to the electronic configuration of a noble gas is
replaced with the symbol of that noble gas in square brackets. Therefore, the abbreviated electron
configuration of sodium is [Ne]3s1 (the electron configuration of neon is 1s22s22p6, which can be
abbreviated to [He]2s22p6).
Electron Configurations are useful for:
• Determining the valency of an element.
• Predicting the properties of a group of elements (elements with similar electron
configurations tend to exhibit similar properties).
• Interpreting atomic spectra.
This notation for the distribution of electrons in the atomic orbitals of atoms came into practice
shortly after the Bohr model of the atom was presented by Ernest Rutherford and Niels Bohr in
the year 1913.
Writing Electron Configurations
Shells
The maximum number of electrons that can be accommodated in a shell is based on the principal
quantum number (n). It is represented by the formula 2n2, where ‘n’ is the shell number. The
shells, values of n, and the total number of electrons that can be accommodated are tabulated
below.
Shell and ‘n’ value Maximum electrons present in the shell
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
Subshells
• The subshells into which electrons are distributed are based on the azimuthal quantum
number (denoted by ‘l’).
• This quantum number is dependent on the value of the principal quantum number, n.
Therefore, when n has a value of 4, four different subshells are possible.
• When n=4. The subshells correspond to l=0, l=1, l=2, and l=3 and are named the s, p, d,
and f subshells, respectively.
• The maximum number of electrons that can be accommodated by a subshell is given by
the formula 2*(2l + 1).
• Therefore, the s, p, d, and f subshells can accommodate a maximum of 2, 6, 10, and 14
electrons, respectively.
All the possible subshells for values of n up to 4 are tabulated below.
Principle Quantum Value of Azimuthal Resulting Subshell in the
Number Value Quantum Number Electron Configuration
n=1 l=0 1s
n=2 l=0 2s
l=1 2p
n=3 l=0 3s
l=1 3p
l=2 3d
n=4 l=0 4s
l=1 4p
l=2 4d
l=3 4f
Thus, it can be understood that the 1p, 2d, and 3f orbitals do not exist because the value of the
azimuthal quantum number is always less than that of the principal quantum number.
Notation
• The electron configuration of an atom is written with the help of subshell labels.
• These labels contain the shell number (given by the principal quantum number), the
subshell name (given by the azimuthal quantum number) and the total number of
electrons in the subshell in superscript.
• For example, if two electrons are filled in the ‘s’ subshell of the first shell, the resulting
notation is ‘1s2’.
• With the help of these subshell labels, the electron configuration of magnesium (atomic
number 12) can be written as 1s2 2s2 2p6 3s2.
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.
Salient Features of the Aufbau Principle
• According to the Aufbau principle, electrons first occupy those
orbitals whose energy is the lowest. This implies that the electrons
enter the orbitals having higher energies only when orbitals with
lower energies have been completely filled.
• The order in which the energy of orbitals increases can be
determined with the help of the (n+l) rule, where the sum of the
principal and azimuthal quantum numbers determines the energy
level of the orbital.
• Lower (n+l) values correspond to lower orbital energies. If two
orbitals share equal (n+l) values, the orbital with the lower n value
is said to have lower energy associated with it.
• The order in which the orbitals are filled with electrons is: 1s, 2s,
2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, and
so on.
Exceptions
The electron configuration of chromium is [Ar]3d54s1 and not [Ar]3d44s2 (as suggested by the
Aufbau principle). This exception is attributed to several factors such as the increased stability
provided by half-filled subshells and the relatively low energy gap between the 3d and the 4s
subshells.
The energy gap between the different subshells is illustrated below.
Half-filled subshells feature lower electron-electron repulsions in the orbitals, thereby increasing
the stability. Similarly, completely filled subshells also increase the stability of the atom.
Therefore, the electron configurations of some atoms disobey the Aufbau principle (depending
on the energy gap between the orbitals).
For example, copper is another exception to this principle with an electronic configuration
corresponding to [Ar]3d104s1. This can be explained by the stability provided by a completely
filled 3d subshell.
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).
An illustration detailing the manner in which electrons are filled in compliance with Hund’s rule
of maximum multiplicity is provided above.
Electron Configuration for All Elements in the Periodic Table
Element Electrons Electronic Configuration
Hydrogen (H) 1 1s1
Helium (He) 2 1s2
Lithium (Li) 3 1s2 2s1
Beryllium (Be) 4 1s2 2s2
Boron (B) 5 1s2 2s2 2p1
Carbon (C) 6 1s2 2s2 2p2
Nitrogen (N) 7 1s2 2s2 2p3
Oxygen (O) 8 1s2 2s2 2p4
Fluorine (F) 9 1s2 2s2 2p5
Neon (Ne) 10 1s2 2s2 2p6
Sodium (Na) 11 1s2 2s2 2p6 3s1
Magnesium (Mg) 12 1s2 2s2 2p6 3s2
Aluminum (Al) 13 1s2 2s2 2p6 3s23p1
Silicon (Si) 14 1s2 2s2 2p6 3s23p2
Phosphorous (P) 15 1s2 2s2 2p6 3s23p3
Sulfur (S) 16 1s2 2s2 2p6 3s23p4
Chlorine (Cl) 17 1s2 2s2 2p6 3s23p5
Argon (Ar) 18 1s2 2s2 2p6 3s23p6
Potassium (K) 19 1s2 2s2 2p6 3s23p6 4s1
Calcium (Ca) 20 1s2 2s2 2p6 3s23p6 4s2
Scandium (Sc) 21 1s2 2s2 2p6 3s23p6 4s2 3d1
Titanium (Ti) 22 1s2 2s2 2p6 3s23p6 4s2 3d2
Vanadium (V) 23 1s2 2s2 2p6 3s23p6 4s2 3d3
Chromium (Cr) 24 1s2 2s2 2p6 3s23p6 4s1 3d5
Manganese (Mn) 25 1s2 2s2 2p6 3s23p6 4s2 3d5
Iron (Fe) 26 1s2 2s2 2p6 3s23p6 4s2 3d6
Cobalt (Co) 27 1s2 2s2 2p6 3s23p6 4s2 3d7
Nickel (Ni) 28 1s2 2s2 2p6 3s23p6 4s2 3d8
Copper (Cu) 29 1s2 2s2 2p6 3s23p6 4s1 3d10
Zinc (Zn) 30 1s2 2s2 2p6 3s23p6 4s2 3d10