MDC:-Chemistry

1. Atomic Structure:-
 Bohr's Atomic Model

Following the discoveries of hydrogen emission spectra and the photoelectric effect, the
Danish physicist Niels Bohr (1885-1962) proposed a new model of the atom in 1915. Bohr
proposed that electrons do not radiate energy as they orbit the nucleus, but exist in states of
constant energy that he called stationary states. This means that the electrons orbit at
fixed distances from the nucleus (see below). Bohr's work was primarily based on the
emission spectra of hydrogen. This is also referred to as the planetary model of the atom. It
explained the inner workings of the hydrogen atom. Bohr was awarded the Nobel Prize in
physics in 1922 for his work.

Bohr's atomic model hydrogen emission spectra.

Bohr explained that electrons can be moved into different orbits with the addition of
energy. When the energy is removed, the electrons return back to their ground state,
emitting a corresponding amount of energy—a quantum of light, or photon. This was the
basis for what later became known as quantum theory. This is a theory based on the
principle that matter and energy have the properties of both particles and waves. It
accounts for a wide range of physical phenomena, including the existence of discrete
packets of energy and matter, the uncertainty principle, and the exclusion principle.

According to the Bohr model, often referred to as a planetary model, the electrons encircle
the nucleus of the atom in specific allowable paths called orbits. When the electron is in one
of these orbits, its energy is fixed. The ground state of the hydrogen atom, where its energy
is lowest, is when the electron is in the orbit that is closest to the nucleus. The orbits that
are further from the nucleus are all of successively greater energy. The electron is not
allowed to occupy any of the spaces in between the orbits. An everyday analogy to the Bohr
model is the rungs of a ladder. As you move up or down a ladder, you can only occupy
specific rungs and cannot be in the spaces in between rungs. Moving up the ladder increases
your potential energy, while moving down the ladder decreases your energy.

Bohr's work had a strong influence on our modern understanding of the inner workings of
the atom. However, his model worked well as an explanation for the emissions of the
hydrogen atom, but was seriously limited when applied to other atoms. Shortly after Bohr
published his planetary model of the atom, several new discoveries were made, which
resulted in, yet again, a revised view of the atom.
  Bohrs Theory of Hydrogen Atoms

Bohr's theory of the hydrogen atom, proposed by Niels Bohr in 1913, is a key milestone in the
development of quantum mechanics. Niels Bohr’s model initially considered only the principal
quantum number (n), which broadly defined the energy levels as n = 1, 2, 3, etc. However, Bohr's
model was primarily effective for the hydrogen atom and didn't fully address more complex
atoms.

Bohr’s model retained the planetary model of electrons orbiting a central nucleus but introduced
quantization to overcome the limitations of the earlier Rutherford model, thus marking a
significant advancement in atomic physics.

1.0Fundamental Postulates of Bohr’s Theory

Bohr’s theory is built on several postulates that deviate from classical physics to incorporate
quantum phenomena:

Bohr’s theory is built on several groundbreaking postulates that deviate from classical physics to
incorporate quantum phenomena:

Quantized Orbits

Bohr proposed that electrons in an atom can only occupy certain fixed orbits without radiating
energy. These orbits, known as "stationary states," have quantized angular momenta and defined
energy levels.

Energy Stability and Quantum Jumps

The energy of an electron in a stationary state is constant over time. The electron only changes its
energy state through a process known as a quantum jump. When an electron absorbs a specific
quantity of energy, it moves to a higher energy orbit (excitation), and it emits energy when it
returns to a lower energy orbit (relaxation).

Bohr’s Frequency Rule for Emitted or Absorbed Radiation

The frequency of radiation emitted or absorbed due to an electron transitioning between two
energy states is directly related to the energy difference between those states.

Equation:

ν=hΔE=hE2−E1

where 𝛎 is the frequency of the emitted or absorbed radiation, E1 and E2 are the energies of the
initial and final orbits respectively, and h is Planck’s constant.

This equation, commonly referred to as Bohr's frequency condition, implies that the energy
difference between the initial and final orbits (denoted as ΔE) determines the frequency of the
emitted or absorbed photon. This relationship is critical for the production of atomic spectra,
specifically the hydrogen spectral lines which Bohr’s model accurately predicted using the
known values of h and the measured spectral lines.

Quantization of Angular Momentum:

The angular momentum of an electron in any stationary state (orbit) is quantized, meaning it can
only take specific, discrete values.

mevr=n2πh

This postulate stipulates that n can be any positive integer (1, 2, 3, ...), and each value of n
corresponds to a specific orbit where the electron’s angular momentum is n. The quantization of
angular momentum restricts the electron to certain allowed orbits. This constraint is fundamental
to why electrons do not spiral into the nucleus and why atoms have stable, defined energy levels.

2.0Energy levels of Hydrogen Atom

The Bohr model of the hydrogen atom provides a clear depiction of the energy levels associated
with the electron's orbits around the nucleus. It describes electrons in quantized energy levels,
each corresponding to a principal quantum number (n).

These levels are calculated using

En=−n213.6Z2eV/atom

where 13.598 eV is the ionization energy necessary to remove the electron from the atom.

In this model, electrons orbit the nucleus in distinct layers or shells, with the ground state (n=1)
having an energy of -13.6 eV. As n increases, the energy levels become less negative, indicating
a decrease in the electron's binding to the nucleus.

This quantization helps explain the spectral lines specific to hydrogen and is visualized as
concentric circles around the nucleus, with the innermost circle representing the ground state.
The ionization energy marks the energy required to liberate the electron completely, set at 13.598
eV for the transition from the lowest energy state to complete freedom (E=0 eV).

3.0Hydrogen Spectrum

The hydrogen spectrum, which consists of emission and absorption lines, provides crucial
insights into the atomic structure of hydrogen and supports the Bohr model of the atom. Here’s a
brief overview of the key elements of the hydrogen spectrum:

1. Line Spectra:

When hydrogen gas is excited (by heating or applying an electric current), the electrons in the
hydrogen atoms absorb energy and move to higher energy levels. When these electrons return to
lower energy levels, they emit light of specific wavelengths , creating a series of spectral lines.

2. Lyman Series:

Occurs when an electron transitions from higher energy levels (n≥2n) to the first energy level
(n=1). These emissions are in the ultraviolet region of the electromagnetic spectrum.

3. Balmer Series:

Represents transitions from higher energy levels (n≥3n) to the second energy level (n=2). These
are the most well-known, occurring in the visible spectrum and responsible for the distinctive red
(H-alpha), blue-green, and violet hydrogen lines commonly observed in laboratory spectra.

4. Paschen Series:

Involves transitions from higher energy levels to the third energy level (n=3). These lines are in
the infrared part of the spectrum.

5. Brackett and Pfund Series:

These series represent transitions to the fourth (n=4) and fifth (n=5) energy levels, respectively,
and also lie in the infrared spectrum.
Each series can be mathematically described by the Rydberg formula:

λ1=RH(n121−n221)

where λ is the wavelength of the emitted or absorbed light, RH is the Rydberg constant
(approximately 1.09737 x 107 m−1), n1 is the lower energy level, and n2 is the higher energy level.

4.0Limitations of Bohr’s Model

Bohr’s model of the hydrogen atom was a significant improvement over Rutherford’s model,
providing explanations for the stability and spectral lines of hydrogen and hydrogen-like ions
such as He+, Li2+, and Be3+. However, despite its successes, Bohr’s model had significant
limitations:

1. Inability to Explain Spectral Fine Structure:

Bohr's model was unable to explain the finer details of the hydrogen spectrum, such as doublet
lines—two closely spaced spectral lines—observed with advanced spectroscopic techniques.
These details are attributed to the fine structure due to electron spin and relativistic effects, which
Bohr’s model does not consider.

2. Failure with Multi-Electron Systems:

The model’s approach fails when applied to atoms with more than one electron, such as helium
(He). Bohr’s theory assumes a single electron moving in an orbit around a nucleus, which
simplifies the interaction dynamics that are critical in multi-electron atoms. For instance, it
cannot account for electron-electron repulsion and more complex quantum mechanical
interactions.

3. Zeeman and Stark Effects:

Bohr’s model could not explain the splitting of spectral lines when an atom is placed in a
magnetic field (Zeeman effect) or an electric field (Stark effect). These phenomena involve
interactions between atomic electrons and external fields, revealing limitations in Bohr’s
treatment of electron orbits and energy levels as strictly quantized without considering external
influences.

4. Molecular Formation:

Bohr’s model does not address how atoms form chemical bonds to create molecules. The model
is centered on single atoms and their internal electron dynamics, lacking the framework to
explore interatomic interactions and bonding, which are crucial for understanding molecular
chemistry.

Electromagnetic radiation is a form of energy that is produced by oscillating electric

and magnetic disturbance, or by the movement of electrically charged particles traveling
through a vacuum or matter. The electric and magnetic fields come at right angles to each
other and combined wave moves perpendicular to both magnetic and electric oscillating
fields thus the disturbance. Electron radiation is released as photons, which are bundles of
light energy that travel at the speed of light as quantized harmonic waves. This energy is
then grouped into categories based on its wavelength into the electromagnetic spectrum.
These electric and magnetic waves travel perpendicular to each other and have certain
characteristics, including amplitude, wavelength, and frequency.

General Properties of all electromagnetic radiation:

 Electromagnetic radiation can travel through empty space. Most other types of
waves must travel through some sort of substance. For example, sound waves need
either a gas, solid, or liquid to pass through in order to be heard.
 The speed of light is always a constant. (Speed of light : 2.99792458 x 108 m s-1)
 Wavelengths are measured between the distances of either crests or troughs. It is
usually characterized by the Greek symbol λλ.

Waves and their Characteristics

Fig. 1 & 2: Electromagnetic Waves

 Fig. 3: An EM Wave

Amplitude

Amplitude is the distance from the maximum vertical displacement of the wave to the
middle of the wave. This measures the magnitude of oscillation of a particular wave. In
short, the amplitude is basically the height of the wave. Larger amplitude means higher
energy and lower amplitude means lower energy. Amplitude is important because it tells
you the intensity or brightness of a wave in comparison with other waves.

Wavelength
Wavelength (λλ) is the distance of one full cycle of the oscillation. Longer wavelength waves such as
radio waves carry low energy; this is why we can listen to the radio without any harmful
consequences. Shorter wavelength waves such as x-rays carry higher energy that can be hazardous
to our health. Consequently lead aprons are worn to protect our bodies from harmful radiation
when we undergo x-rays. This wavelength frequently relationship is characterized by:

c=λν(1)(1)c=λν

where
c is the speed of light,
λλ is wavelength, and
νν is frequency.

Shorter wavelength means greater frequency, and greater frequency means higher energy.
Wavelengths are important in that they tell one what type of wave one is dealing with.

Fig. 4: Different Wavelengths and Frequencies

 Remember, Wavelength tells you the type of light and Amplitude tells you about the
intensity of the light

Frequency

Frequency is defined as the number of cycles per second, and is expressed as sec-1 or Hertz
(Hz). Frequency is directly proportional to energy and can be express as:

E=hν(2)(2)E=hν

where

 E is energy,
 h is Planck's constant, (h= 6.62607 x 10-34 J), and
 νν is frequency.

Period

Period (T) is the amount of time a wave takes to travel one wavelength; it is measured in
seconds (s).

Velocity

The velocity of wave in general is expressed as:

velocity=λν(3)(3)velocity=λν

For Electromagnetic wave, the velocity in vacuum

is 2.99×108m/s2.99×108m/s or 186,282186,282 miles/second.

Electromagnetic spectrum

Figure 24.5.1: Electromagnetic spectrum with light highlighted.

As a wave’s wavelength increases, the frequency decreases, and as wave’s wavelength
decreases, the frequency increases. When electromagnetic energy is released as the energy
level increases, the wavelength decreases and frequency decreases. Thus, electromagnetic
radiation is then grouped into categories based on its wavelength or frequency into the
electromagnetic spectrum. The different types of electromagnetic radiation shown in the
electromagnetic spectrum consists of radio waves, microwaves, infrared waves, visible
light, ultraviolet radiation, X-rays, and gamma rays. The part of the electromagnetic
spectrum that we are able to see is the visible light spectrum.

Fig. 6: Electromagnetic Spectrum with Radiation Types

Radiation Types

Radio Waves are approximately 103 m in wavelength. As the name implies, radio waves are
transmitted by radio broadcasts, TV broadcasts, and even cell phones. Radio waves have the
lowest energy levels. Radio waves are used in remote sensing, where hydrogen gas in space
releases radio energy with a low frequency and is collected as radio waves. They are also
used in radar systems, where they release radio energy and collect the bounced energy
back. Especially useful in weather, radar systems are used to can illustrate maps of the
surface of the Earth and predict weather patterns since radio energy easily breaks through
the atmosphere. ;

Microwaves can be used to broadcast information through space, as well as warm food.
They are also used in remote sensing in which microwaves are released and bounced back
to collect information on their reflections.

Microwaves can be measured in centimeters. They are good for transmitting information
because the energy can go through substances such as clouds and light rain. Short
microwaves are sometimes used in Doppler radars to predict weather forecasts.

Infrared radiation can be released as heat or thermal energy. It can also be bounced back,
which is called near infrared because of its similarities with visible light energy. Infrared
 Radiation is most commonly used in remote sensing as infrared sensors collect thermal
energy, providing us with weather conditions.

This picture represents a snap shot in mid-infrared light.

Visible Light is the only part of the electromagnetic spectrum that humans can see with an
unaided eye. This part of the spectrum includes a range of different colors that all represent
a particular wavelength. Rainbows are formed in this way; light passes through matter in
which it is absorbed or reflected based on its wavelength. Thus, some colors are reflected
more than other, leading to the creation of a rainbow.

Color Region Wavelength (nm)

Violet 380-435

Blue 435-500

Cyan 500-520

Green 520-565

Yellow 565-590

Orange 590-625

Red 625-740

Fig. 7: The color regions of the Visible Spectrum

Fig. 8: Dispersion of Light Through A Prism

Ultraviolet, Radiation, X-Rays, and Gamma Rays are all related to events occurring in space.
UV radiation is most commonly known because of its severe effects on the skin from the
sun, leading to cancer. X-rays are used to produce medical images of the body. Gamma Rays
can used in chemotherapy in order to rid of tumors in a body since it has such a high energy
level. The shortest waves, Gamma rays, are approximately 10-12 m in wavelength. Out this
huge spectrum, the human eyes can only detect waves from 390 nm to 780 nm.
Equations of Waves

The mathematical description of a wave is:

y=Asin(kx−ωt)(4)(4)y=Asin⁡(kx−ωt)

where A is the amplitude, k is the wave number, x is the displacement on the x-axis.

k=2πλ(5)(5)k=2πλ

where λλ is the wavelength. Angular frequency described as:

ω=2πν=2πT(6)(6)ω=2πν=2πT

where νν is frequency and period (T) is the amount of time for the wave to travel one
wavelength.

Interference

An important property of waves is the ability to combine with other waves. There are two
type of interference: constructive and destructive. Constructive interference occurs when
two or more waves are in phase and and their displacements add to produce a higher
amplitude. On the contrary, destructive interference occurs when two or more waves are
out of phase and their displacements negate each other to produce lower amplitude.

Figure 9 & 10: Constructive and Destructive Interference

Interference can be demonstrated effectively through the double slit experiment. This
experiment consists of a light source pointing toward a plate with one slit and a second
plate with two slits. As the light travels through the slits, we notice bands of alternating
intensity on the wall behind the second plate. The banding in the middle is the most intense
because the two waves are perfectly in phase at that point and thus constructively interfere.
The dark bands are caused by out of phase waves which result in destructive interference.
This is why you observe nodes on figure 4. In a similar way, if electrons are used instead of
light, electrons will be represented both as waves and particles.

Fig. 11 & 12: Double-Slit Interference Experiment

Wave-Particle Duality

Electromagnetic radiation can either acts as a wave or a particle, a photon. As a wave, it is

represented by velocity, wavelength, and frequency. Light is an EM wave since the speed of
EM waves is the same as the speed of light. As a particle, EM is represented as a photon,
which transports energy. When a photon is absorbed, the electron can be moved up or
down an energy level. When it moves up, it absorbs energy, when it moves down, energy is
released. Thus, since each atom has its own distinct set of energy levels, each element emits
and absorbs different frequencies. Photons with higher energies produce shorter
wavelengths and photons with lower energies produce longer wavelengths.

Fig. 13: Photon Before and After Emission

When an electron transitions from a higher (excited) to a lower (normal) state, it generates
electromagnetic radiation known as the hydrogen spectrum. It is complicated because it
contains more than three lines visible to the human eye and serves as vital proof that an
atom’s electronic structure is quantized. It is very important in astronomy since hydrogen
makes up the majority of the universe.

Hydrogen Spectrum

A hydrogen atom consists of an electron and a proton, and the force of attraction between the
electron and nuclear proton leads to a set of energy levels or quantum states. Each energy state
has its energy and physical attributes. These states were first described by Neil Bohr, and he
called them orbits. However, his model was later modified into a quantum mechanics model,
and these energy levels were called atomic orbitals.

The hydrogen spectrum appears when the electron of the hydrogen atom jumps from a higher
energy level to a lower energy level. These two states are differentiated by n (higher energy
state) and n’ (lower energy state). The intensity of emitted light particles or photons directly
depends on the difference in the two energy levels.

Excitation of the Electron

Electrons are caused to excite by applying energy. They jump towards higher energy levels
by receiving enough energy from an external source. This minimum energy required to put
electrons into the excited state is termed excitation energy. The intensity of excitation
energy is dependent on the distance of the electron from the nucleus. Lower the distance of
the electron from the nucleus makes it experience high nuclear attraction. Hence, the value
of excitation energy required is higher.

Frequency and Wavelength Relation

The frequency and wavelength are related to each other as follows:

c=λv,

where ‘c’ is the velocity of light,

‘λ’ is the wavelength,

and ‘v’ is the frequency.

We can also write this equation as

λ=c/v

or, v=c/λ.

It implies that the wavelength and the frequency are inversely proportional to each other.

Hydrogen Spectrum Wavelength

When a photon is sent towards the hydrogen atom with a high frequency, it causes the
electron to jump across lower energy levels of the hydrogen atom. Consequently, the
transmission of light with different wavelengths occurs. Each wavelength corresponds to a
transition between specific quantum states. For instance, the transition between the third
and second energy levels imparts light of 656 nm wavelength.

Hydrogen Emissions Spectrum Series

The hydrogen atom emits light due to the transition of electrons between two energy levels.
The different wavelengths of the emission spectrum are calculated using Rydberg’s formula.

This emission spectrum is classified into different series:

Lyman Series

It is the series of emitted light if the transition occurs between the first and any other
energy level.

Balmer Series

It is the series of transitions between the second and any other energy level.

Paschen Series

It is the transition between the third and any other energy level.

Bracket Series

It is the transition between the fourth and any other energy state.

Pfund Series

It is the transition between the fifth and any other energy state.
Hydrogen Emission Spectrum Formula

The hydrogen spectrum contains many different spectral lines. These lines have different
wavelengths. In 1890, Rydberg gave the general formula to calculate the wavelengths of these
lines in a very simplified method.

The equation for the wavelengths of these spectral lines is described as:

1λ=R(1n12–1n22)1λ=R(1n12–1n22)

Where, R stands for Rydberg’s constant = 109677 per cm.

n1n1 and n2n2 = whole numbers for a particular series.

The value of n1n1 is constant. Whereas, n2n2 can adopt different values for a particular series.

Limitations of Bohr’s Atomic Model

The nuclear model appeared in 1915. He made sense of electrons and their circle in his
hypothesis. But there are several limitations like “Bohr’s model of an atom” fails to explain
the “Zeeman effect” and violates the “Heisenberg uncertainty principle”.

Notwithstanding, a few limitations were seen in Bohr’s Atomic Model. These are:

 Bohr’s model was applied only to the unimolecular systems.

 It could not explain the spectral line spectrum of Hydrogen Atoms.
 Bohr’s model of an atom failed to explain the “Zeeman Effect”.
 It doesn’t make sense of the stark impact, i.e. the effect of an electric field on the
spectrum of Hydrogen atoms.
 It violates the Heisenberg Uncertainty Principle.
 It couldn’t make sense that the spectra were from bigger particles.

De Broglie’s theory is the one of the most fundamental theories which gives a
direction to quantum mechanics from classical physics. It describes the dual nature of
matter, i.e., a matter can behave like both particle and wave. The phenomenon of a beam of
light which diffracted just like a wave is explained by this theory.

In 1924 a French physicist, Louis de Brogile gave the proposal about the wave nature of the
particle.It was observed that the electron which we usually think of as a particle may in
some situations behave like a wave.
Body ___Observing the wave nature of the electron :

De Broglie’s proposal of De Broglie’s theory was a bold one, made at the time when there
was no direct experimental evidence that particles have wave characteristics. But within a
few years his ideas were verified by diffraction experiments. There are also some other
experiments like three dimensional diffraction grating by X ray, Bell Telephone
Laboratories experiment and others like these which prove the wave nature of the
microscopic particle which is in motion.

Electron Waves And The De Broglie’s Theory :

If a particle acts as a wave, it should have a wavelength and a frequency. According to De

Broglie’s theory free particle with rest mass m, moving with non-relativistic speed v, should
have a wavelength related to its momentum p=mv in exactly the same way as for a photon,
as expressed by the equation:

If the de Broglie picture is correct and matter has wave-like aspects, you might wonder why
we don’t see these aspects in everyday life. As an example, we know that waves diffract
through a single slit. Yet when we walk through a doorway (A kind of a single slit), we dont
worry about our body diffracting!

The main reason we don’t see these effects on human scales is that Planck’s constant h has
such a minuscule value. As a result, the de Broglie wavelengths of even the smallest
ordinary objects that you can see are extremely small, and the wave effects are
unimportant. For instance, what is the wavelength of a falling grain of sand? If the grain’s
mass is 510-10 kg and its diameter is 0.07mm = 710-5 m, it will fall in air with a terminal
speed of about 0.4 m/s. The magnitude of its momentum is p = mv =(510-10)(0.4m/s)=
210-10kg.m/s. Now if we calculate the wavelength then it will be

So this wavelength is very small, that’s why we cannot observe this in our real life.

A more massive and high moving body has more momentum and even smaller de broglie
wavelength.The effect of such tiny wavelengths are so small that they are never noticed in
our daily life.

Application Of the De Broglie’s theory :

1.Electron microscope

An electron microscope offers an important and interesting example of the dual nature of
electrons. An electron beam can be used to form an Image of an object much similar to that
of light. So here the wave nature of the electron comes into the picture for image formation.

Which is an application of De Broglie’s theory.

2.Atomic Spectra

Every neutral atom consists of at least one electron. So when a material is heated it emits
light, and different materials have different types of the light. This is because of the dual
nature of the matter.Again which is proved by De Broglie’s theory.

3. Bohr’s Atomic Model

According to Bohr’s Atomic Model the angular momentum of the electron is quantized.
Which proves that both Bohr’s quantization of angular momentum and De Brogliers theory
are interrelated.

Heisenberg's Uncertainty Principle states that there is inherent uncertainty in the act of
measuring a variable of a particle. Commonly applied to the position and momentum of a
particle, the principle states that the more precisely the position is known the more
uncertain the momentum is and vice versa. This is contrary to classical Newtonian physics
which holds all variables of particles to be measurable to an arbitrary uncertainty given
good enough equipment. The Heisenberg Uncertainty Principle is a fundamental theory in
quantum mechanics that defines why a scientist cannot measure multiple quantum
variables simultaneously. Until the dawn of quantum mechanics, it was held as a fact that all
variables of an object could be known to exact precision simultaneously for a given
moment. Newtonian physics placed no limits on how better procedures and techniques
could reduce measurement uncertainty so that it was conceivable that with proper care and
accuracy all information could be defined. Heisenberg made the bold proposition that there
is a lower limit to this precision making our knowledge of a particle inherently uncertain.

More specifically, if one knows the precise momentum of the particle, it is impossible to
know the precise position, and vice versa. This relationship also applies to energy and time,
in that one cannot measure the precise energy of a system in a finite amount of time.
Uncertainties in the products of “conjugate pairs” (momentum/position) and (energy/time)
were defined by Heisenberg as having a minimum value corresponding to Planck’s constant
divided by 4π4π. More clearly:

ΔpΔx≥h4π(1)(1)ΔpΔx≥h4π

ΔtΔE≥h4π(2)(2)ΔtΔE≥h4π

Where ΔΔ refers to the uncertainty in that variable and h is Planck's constant.

Aside from the mathematical definitions, one can make sense of this by imagining that the
more carefully one tries to measure position, the more disruption there is to the system,
resulting in changes in momentum. For example compare the effect that measuring the
position has on the momentum of an electron versus a tennis ball. Let’s say to measure
these objects, light is required in the form of photon particles. These photon particles have a
measurable mass and velocity, and come into contact with the electron and tennis ball in
order to achieve a value in their position. As two objects collide with their respective
momenta (p=m*v), they impart theses momenta onto each other. When the photon contacts
the electron, a portion of its momentum is transferred and the electron will now move
relative to this value depending on the ratio of their mass. The larger tennis ball when
measured will have a transfer of momentum from the photons as well, but the effect will be
lessened because its mass is several orders of magnitude larger than the photon. To give a
more practical description, picture a tank and a bicycle colliding with one another, the tank
portraying the tennis ball and the bicycle that of the photon. The sheer mass of the tank
although it may be traveling at a much slower speed will increase its momentum much
higher than that of the bicycle in effect forcing the bicycle in the opposite direction. The final
result of measuring an object’s position leads to a change in its momentum and vice versa.
All Quantum behavior follows this principle and it is important in determining spectral line
widths, as the uncertainty in energy of a system corresponds to a line width seen in regions
of the light spectrum explored in Spectroscopy.

What does it mean?

It is hard to imagine not being able to know exactly where a particle is at a given moment. It
seems intuitive that if a particle exists in space, then we can point to where it is; however,
the Heisenberg Uncertainty Principle clearly shows otherwise. This is because of the wave-
like nature of a particle. A particle is spread out over space so that there simply is not a
precise location that it occupies, but instead occupies a range of positions. Similarly, the
momentum cannot be precisely known since a particle consists of a packet of waves, each of
which have their own momentum so that at best it can be said that a particle has a range of
momentum.

A wave packet in space

Let's consider if quantum variables could be measured exactly. A wave that has a perfectly
measurable position is collapsed onto a single point with an indefinite wavelength and
therefore indefinite momentum according to de Broglie's equation. Similarly, a wave with a
perfectly measurable momentum has a wavelength that oscillates over all space infinitely
and therefore has an indefinite position.

You could do the same thought experiment with energy and time. To precisely measure a
wave's energy would take an infinite amount of time while measuring a wave's exact
instance in space would require to be collapsed onto a single moment which would have
indefinite energy.

Consequences

The Heisenberg Principle has large bearing on practiced science and how experiments are
designed. Consider measuring the momentum or position of a particle. To create a
measurement, an interaction with the particle must occur that will alter it's other variables.
For example, in order to measure the position of an electron there must be a collision
between the electron and another particle such as a photon. This will impart some of the
second particle's momentum onto the electron being measured and thereby altering it. A
more accurate measurement of the electron's position would require a particle with a
smaller wavelength, and therefore be more energetic, but then this would alter the
momentum even more during collision. An experiment designed to determine momentum
would have a similar effect on position. Consequently, experiments can only gather
information about a single variable at a time with any amount of accuracy.

Quantum Number
An atom consists of a large number of orbitals which are distinguished from each other on the
basis of their shape, size and orientation in space. The orbital characteristics are used to define
the state of an electron completely and are expressed in terms of three numbers as stated,
Principal quantum number, Azimuthal quantum number and Magnetic quantum number and
Spin Quantum number.

Quantum number are those numbers that designate and distinguish various atomic
orbitals and electrons present in an atom. A set of four numbers through which we can get the
complete information about all the electrons in an atom, be it energy, location, space, type
of orbital occupied, and even the orientation of that orbital is called Quantum Numbers.

Principal Quantum Number

The Principal Quantum Number represents the principal energy level or shell in which an
electron revolves around the nucleus. It is denoted by the letter n and can have any integral
value except the 0 i.e. n = 1, 2, 3, 4 … ….etc. The energies of the various principal shells will
follow the sequence as :

K < L < M < N < O…..

1 < 2 < 3 < 4 < 5…….

Azimuthal Quantum Number

Azimuthal quantum number, also known as orbital quantum number determines the subshell
to which an electron belongs. As a matter of result, the number of electronic jump increases
and the number of lines at the same time.
 For a given value of n, it can have any integral value ranging from 0 to n – 1.

 For the 1st Shell, say K, n =1, you can have only one value i.e. l = 0

 For the 2nd Shell, say L, n = 2, you can have two values i.e. l = 0 and 1

 For the 3rd Shell, say M, n = 3, you can have three values i.e. l = 0, 1 and 2

 For the 4th shells, say N, n = 4, you can have 4 values i.e. l = 0, 1, 2 and 3
Magnetic Quantum Number
Magnetic Quantum Number denoted by the symbol m is what represents the orientation of
atomic orbital in space. The value of the Magnetic Quantum Number, m, depends on the value
of l. Magnetic Quantum Number can have a total number of (2l + 1).

Sublevel l ml

s 0 0

p 1 -1, 0, +1

d 2 -2, -1, 0, +1, +2

f 3 -3, -2, -1, 0, +1, +2, +3

Spin Quantum Number

Spin Quantum Number represents the direction of the spin of the electrons. This can either be
in the direction of clockwise or even anti-clockwise. Spin Quantum Number is denoted by the
symbol s. It can have about only two values i.e. +1/2 or -1/2.

Electron Configuration

The electron configuration of an atomic species (neutral or ionic) allows us to understand

the shape and energy of its electrons. Many general rules are taken into consideration when
assigning the "location" of the electron to its prospective energy state, however these
assignments are arbitrary and it is always uncertain as to which electron is being described.
Knowing the electron configuration of a species gives us a better understanding of
its bonding ability, magnetism and other chemical properties.

Introduction

The electron configuration is the standard notation used to describe the electronic
structure of an atom. Under the orbital approximation, we let each electron occupy an
orbital, which can be solved by a single wavefunction. In doing so, we obtain three quantum
numbers (n,l,ml), which are the same as the ones obtained from solving the Schrödinger's
equation for Bohr's hydrogen atom. Hence, many of the rules that we use to describe the
electron's address in the hydrogen atom can also be used in systems involving multiple
electrons. When assigning electrons to orbitals, we must follow a set of three rules: the
Aufbau Principle, the Pauli-Exclusion Principle, and Hund's Rule.

The wavefunction is the solution to the Schrödinger equation. By solving the Schrödinger
equation for the hydrogen atom, we obtain three quantum numbers, namely the principal
quantum number (n), the orbital angular momentum quantum number (l), and the
magnetic quantum number (ml). There is a fourth quantum number, called the spin
magnetic quantum number (ms), which is not obtained from solving the Schrödinger
equation. Together, these four quantum numbers can be used to describe the location of an
electron in Bohr's hydrogen atom. These numbers can be thought of as an electron's
"address" in the atom.

Notation

To help describe the appropriate notation for electron configuration, it is best to do so

through example. For this example, we will use the iodine atom. There are two ways in
which electron configuration can be written:

I: 1s22s22p63s23p64s23d104p65s24d105p5

or

I: [Kr]5s24d105p5

In both of these types of notations, the order of the energy levels must be written by
increased energy, showing the number of electrons in each subshell as an exponent. In the
short notation, you place brackets around the preceding noble gas element followed by the
valence shell electron configuration. The periodic table shows that kyrpton (Kr) is the
previous noble gas listed before iodine. The noble gas configuration encompases the energy
states lower than the valence shell electrons. Therefore, in this case
[Kr]=1s22s22p63s23p64s23d104p6.

Quantum Numbers

Principal Quantum Number (n)

The principal quantum number n indicates the shell or energy level in which the electron is
found. The value of n can be set between 1 to n, where n is the value of the outermost shell
containing an electron. This quantum number can only be positive, non-zero, and integer
values. That is, n=1,2,3,4,..

For example, an Iodine atom has its outmost electrons in the 5p orbital. Therefore, the
principle quantum number for Iodine is 5.
Orbital Angular Momentum Quantum Number (l)

The orbital angular momentum quantum number, l, indicates the subshell of the electron.
You can also tell the shape of the atomic orbital with this quantum number. An s subshell
corresponds to l=0, a p subshell = 1, a d subshell = 2, a f subshell = 3, and so forth. This
quantum number can only be positive and integer values, although it can take on a zero
value. In general, for every value of n, there are n values of l. Furthermore, the value
of l ranges from 0 to n-1. For example, if n=3, l=0,1,2.

So in regards to the example used above, the l values of Iodine for n = 5 are l = 0, 1, 2, 3, 4.

Magnetic Quantum Number (ml)

The magnetic quantum number, ml, represents the orbitals of a given subshell. For a given l,
ml can range from -l to +l. A p subshell (l=1), for instance, can have three orbitals
corresponding to ml = -1, 0, +1. In other words, it defines the px, py and pzorbitals of the p
subshell. (However, the ml numbers don't necessarily correspond to a given orbital. The fact
that there are three orbitals simply is indicative of the three orbitals of a p subshell.) In
general, for a given l, there are 2l+1 possible values for ml; and in a n principal shell, there
are n2 orbitals found in that energy level.

Continuing on from out example from above, the ml values of Iodine are ml = -4, -3, -2, -1, 0
1, 2, 3, 4. These arbitrarily correspond to the 5s, 5px, 5py, 5pz, 4dx2-y2, 4dz2, 4dxy, 4dxz, and
4dyz orbitals.

Spin Magnetic Quantum Number (ms)

The spin magnetic quantum number can only have a value of either +1/2 or -1/2. The value
of 1/2 is the spin quantum number, s, which describes the electron's spin. Due to the
spinning of the electron, it generates a magnetic field. In general, an electron with a
ms=+1/2 is called an alpha electron, and one with a ms=-1/2 is called a beta electron. No
two paired electrons can have the same spin value.

Out of these four quantum numbers, however, Bohr postulated that only the principal
quantum number, n, determines the energy of the electron. Therefore, the 3s orbital (l=0)
has the same energy as the 3p (l=1) and 3d (l=2) orbitals, regardless of a difference
in l values. This postulate, however, holds true only for Bohr's hydrogen atom or other
hydrogen-like atoms.

When dealing with multi-electron systems, we must consider the electron-electron

interactions. Hence, the previously described postulate breaks down in that the energy of
the electron is now determined by both the principal quantum number, n, and the orbital
angular momentum quantum number, l. Although the Schrödinger equation for many-
electron atoms is extremely difficult to solve mathematically, we can still describe their
electronic structures via electron configurations.

General Rules of Electron Configuration

There are a set of general rules that are used to figure out the electron configuration of an
atomic species: Aufbau Principle, Hund's Rule and the Pauli-Exclusion Principle. Before
 continuing, it's important to understand that each orbital can be occupied by two electrons
of opposite spin (which will be further discussed later). The following table shows
the possible number of electrons that can occupy each orbital in a given subshell.

subshell number of orbitals total number of possible electrons in each orbital

s 1 2

p 3 (px, py, pz) 6

d 5 (dx2-y2, dz2, dxy, dxz, dyz) 10

f 7 (fz3, fxz2, fxyz, fx(x2-3y2), fyz2, fz(x2-y2), fy(3x2-y2)

14

Using our example, iodine, again, we see on the periodic table that its atomic number is 53
(meaning it contains 53 electrons in its neutral state). Its complete electron configuration is
1s22s22p63s23p64s23d104p65s24d105p5. If you count up all of these electrons, you will see
that it adds up to 53 electrons. Notice that each subshell can only contain the max amount of
electrons as indicated in the table above.

Aufbau Principle

The word 'Aufbau' is German for 'building up'. The Aufbau Principle, also called the
building-up principle, states that electron's occupy orbitals in order of increasing energy.
The order of occupation is as follows:

1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d<7p

Another way to view this order of increasing energy is by using Madelung's Rule:
 Figure 1. Madelung's Rule is a simple generalization which
dictates in what order electrons should be filled in the
orbitals, however there are exceptions such as
copper and chromium.

This order of occupation roughly represents the increasing energy level of the orbitals.
Hence, electrons occupy the orbitals in such a way that the energy is kept at a minimum.
That is, the 7s, 5f, 6d, 7p subshells will not be filled with electrons unless the lower energy
orbitals, 1s to 6p, are already fully occupied. Also, it is important to note that although the
energy of the 3d orbital has been mathematically shown to be lower than that of the 4s
orbital, electrons occupy the 4s orbital first before the 3d orbital. This observation can be
ascribed to the fact that 3d electrons are more likely to be found closer to the nucleus;
hence, they repel each other more strongly. Nonetheless, remembering the order of orbital
energies, and hence assigning electrons to orbitals, can become rather easy when related to
the periodic table.

To understand this principle, let's consider the bromine atom. Bromine (Z=35), which has
35 electrons, can be found in Period 4, Group VII of the periodic table. Since bromine has 7
valence electrons, the 4s orbital will be completely filled with 2 electrons, and the
remaining five electrons will occupy the 4p orbital. Hence the full or expanded electronic
configuration for bromine in accord with the Aufbau Principle is
1s22s22p63s23p64s23d104p5. If we add the exponents, we get a total of 35 electrons,
confirming that our notation is correct.
Hund's Rule

Hund's Rule states that when electrons occupy degenerate orbitals (i.e. same n
and l quantum numbers), they must first occupy the empty orbitals before double
occupying them. Furthermore, the most stable configuration results when the spins are
parallel (i.e. all alpha electrons or all beta electrons). Nitrogen, for example, has 3 electrons
occupying the 2p orbital. According to Hund's Rule, they must first occupy each of the three
degenerate p orbitals, namely the 2px orbital, 2py orbital, and the 2pz orbital, and with
parallel spins (Figure 2). The configuration below is incorrect because the third electron
occupies does not occupy the empty 2pz orbital. Instead, it occupies the half-filled
2px orbital. This, therefore, is a violation of Hund's Rule (Figure 2).

Figure 2. A visual representation of the Aufbau Principle and Hund's Rule. Note that the
filling of electrons in each orbital
(px, py and pz) is arbitrary as long as the electrons are singly filled before having two
electrons occupy the same orbital.
(a)This diagram represents the correct filling of electrons for the nitrogen atom. (b) This
diagramrepresents the incorrect
filling of the electrons for the nitrogen atom.

Pauli-Exclusion Principle

Wolfgang Pauli postulated that each electron can be described with a unique set of four
quantum numbers. Therefore, if two electrons occupy the same orbital, such as the 3s
orbital, their spins must be paired. Although they have the same principal quantum number
(n=3), the same orbital angular momentum quantum number (l=0), and the same magnetic
quantum number (ml=0), they have different spin magnetic quantum numbers (ms=+1/2
and ms=-1/2).

Electronic Configurations of Cations and Anions

The way we designate electronic configurations for cations and anions is essentially similar
to that for neutral atoms in their ground state. That is, we follow the three important rules:
Aufbau Principle, Pauli-exclusion Principle, and Hund's Rule. The electronic configuration of
cations is assigned by removing electrons first in the outermost p orbital, followed by the s
orbital and finally the d orbitals (if any more electrons need to be removed). For instance,
the ground state electronic configuration of calcium (Z=20) is 1s22s22p63s23p64s2. The
calcium ion (Ca2+), however, has two electrons less. Hence, the electron configuration for
Ca2+ is 1s22s22p63s23p6. Since we need to take away two electrons, we first remove
electrons from the outermost shell (n=4). In this case, all the 4p subshells are empty; hence,
we start by removing from the s orbital, which is the 4s orbital. The electron configuration
for Ca2+ is the same as that for Argon, which has 18 electrons. Hence, we can say that both
are isoelectronic.

The electronic configuration of anions is assigned by adding electrons according to Aufbau

Principle. We add electrons to fill the outermost orbital that is occupied, and then add more
electrons to the next higher orbital. The neutral atom chlorine (Z=17), for instance has 17
electrons. Therefore, its ground state electronic configuration can be written as
1s22s22p63s23p5. The chloride ion (Cl-), on the other hand, has an additional electron for a
total of 18 electrons. Following Aufbau Principle, the electron occupies the partially filled 3p
subshell first, making the 3p orbital completely filled. The electronic configuration for Cl-
can, therefore, be designated as 1s22s22p63s23p6. Again, the electron configuration for the
chloride ion is the same as that for Ca2+ and Argon. Hence, they are all isoelectronic to each
other.
2. Periodicity:-
Classification of Elements and Periodicity in Properties

• Genesis of Periodic Classification Dobereiner’s Triads

In 1829, Dobereiner arranged certain elements with similar properties in groups of three in
such a way that the atomic mass of the middle element was nearly the same as the average
atomic masses of the first and the third elements. A few triads proposed by him are listed.

Limitations of Dobereiner’s Trids

The triads given by Dobereiner were helpful in grouping some elements with similar
characteristics together, but he could not arrange all the elements known at that time into
triads.

 Newlands’ Law of Octaves

John Newlands proposed the law of octaves by stating that when elements are arranged
in order of increasing atomic masses, every eighth element has properties similar to the
first. Newlands called it law of octaves because similar relationship exists in the musical
notes also.
This can be illustrated as:
 Limitations of Newlands’ Law of Octaves
(i) This classification was successful only up to the element calcium. After that, every
eighth element did not possess the same properties as the element lying above it in the
same group.
(ii) When noble gas elements were discovered at a later stage, their inclusion in the
table disturbed the entire arrangement.

 Mendeleev’s Periodic Table

Mendeleev’s Periodic Law: The physical and chemical properties of the elements are a
periodic function of their atomic masses. Mendeleev arranged the elements known at
that time in order of increasing atomic masses and this arrangement was called periodic
table.
Elements with similar characteristics were present in vertical rows called groups. The
horizontal rows were known as periods.

 Description of Mendeleev’s Periodic Table:-

I. In the periodic table, the elements are arranged in vertical rows called
groups and horizontal rows known as periods.
II. There are nine groups indicated by Roman Numerals as I, II, III, IV, V, VI, VII,
VIII and zero. Group VIII consists of nine elements which are arranged in
three triads. The zero group contains elements belonging to inert gases or
noble gases and elements present have zero valency.
III. There are seven periods (numbered from 1 to 7) or, horizontal rows in the
Mendeleev’s periodic table.

 Importance of Mendeleev’s Periodic Table

(i) This made the study of the elements quite systematic in the sense that if the
properties of one element in a particular group are known, those of others can be
pridicted.
(ii) This helped to a great extent in the discovery of these elements at a later stage.
(iii) Mendeleev corrected the atomic masses of certain elements with the help of
their expected positions and properties.

 Defects in Mendeleev’s Periodic Table

(i) Hydrogen has been placed in group IA along with alkali metals. But it also
resembles halogens of group VII A in many properties. Thus, its position is the
Mendeleev’s periodic table is controversial.
(ii) Although the elements in the Mendeleev’s periodic table have been arranged in
order of their atomic masses, but in some cases the element with higher atomic mass
precedes the element with lower atomic mass.
(iii) We know that the isotopes of an element have different atomic masses but same
atomic number. Since, periodic table has been framed on the basis of increasing
atomic masses of the elements, different positions must have been allotted to all the
isotopes of a particular element.
(iv) According to Mendeleev, the elements placed in the same group must resemble
in their properties. But there is no similarity among the elements in the two sub-
groups of a particular group.
(v) In some cases, elements with similar properties have been placed in different groups.
(vi) Lanthanoids and actinoids were placed in two separate rows at the bottom of the
periodic table without assigning a proper reason.
(vii) No proper explanation has been offered for the fact that why the elements placed in
group show resemblance in their properties.

 Modern Periodic Law

Physical and chemical properties of the elements are the periodic function of their
atomic numbers.
• Present Form of the Periodic Table (Long form of Periodic Table)
The long form of periodic table, also called Modem Periodic Table, is based on
Modern periodic law. In this table, the elements have been arranged in order of
increasing atomic numbers.
• Nomenclature of Elements with Atomic No. more tha
• Structural Features of the Periodic Table

Groups
The long form of periodic table also consists of the vertical rows called groups.
There are in all 18 groups in the periodic table. Unlike Mendeleev periodic table,
each group is an independent group.

Characteristics of groups:
(i) All the elements present in a group have same general electronic configuration of
the atoms.
(ii) The elements in a group are separated by definite gaps of atomic numbers (2, 8,
8,18, 18,32).
(iii) The atomic sizes of the elements in group increase down the group due to
increase the number of shells.
(iv) The physical properties of the elements such as m.p., b.p. density, solubility etc.,
follow a systematic pattern.
(v) The elements in each group have generally similar chemical properties.

Periods
Horizontal rows in a periodic table are known as periods.
There are in all seven periods in the long form of periodic table.

Characteristics of periods:
(i) In all the elements present in a period, the electrons are filled in the same valence
shell.
(ii) The atomic sizes generally decrease from left to right.
s-Block Elements
General electronic configuration: ns1-2 Characteristics of s-block elements:
(i) All the elements are soft metals.
(ii) They have low melting and boiling points.
(iii) They are highly reactive.
(iv) Most of them impart colours to the flame.
(v) They generally form ionic compounds.
(vi) They are good conductors of heat and electricity. p-Block Elements
General electronic configuration: ns2np1-6

Characteristics of p-block elements:

(i) The compounds of these elements are mostly covalent in nature.
(ii) They show variable oxidation states.
(iii) In moving from left to right in a period, the non-metallic character of the
elements increases.
(iv) The reactivity of elements in a group generally decreases downwards.
(v) At the end of each period is a noble gas element with a closed valence shell
ns2 np6 configuration.
(vi) Metallic character increases as we go down the group.
d-Block Elements
General electronic configuration: (n -1) d1-10 ns0-2
The d-block elements are known as transition elements because they have
incompletely filled d-orbitals in their ground state or in any of the oxidation states.

Characteristics of d-block elements:

(i) They are all metals with high melting and boiling points.
(ii) The compounds of the elements are generally paramagnetic in nature.
(iii) They mostly form coloured ions, exhibit variable valence (oxidation states).
(iv) They are of tenly used as catalysts.

f-Block Elements
General electronic configuration: (n – 2) f1-14 (n -1) d0-1 ns2
They are known as inner transition elements because in the transition elements of
d-block, the electrons are filled in (n – 1) d sub-shell while in the inner transition
elements of f-block the filling of electrons takes place in (n – 2) f subshell, which
happens to be one inner subshell. Characteristics of f-Block elements:
(i) The two rows of elements at the bottom of the Periodic Table, called the
Lanthanoids Ce (Z = 58) – Lu (Z = 71) and Actinoids Th (Z = 90) – Lr (Z = 103).
(ii) These two series of elements are called Inner Transition Elements (f-Block
Elements).
(iii) They are all metals. Within each series, the properties of the elements are quite
similar.
(iv) Most of the elements pf the actinoid series are radio-active in nature.

• Metals
(i) Metals comprise more than 78% of all known elements and appear on the left
side of the Periodic Table.
(ii) Metals are solids at room temperature.
(iii) Metal usually have high melting and boiling points.
(iv) They are good conductors of heat and electricity.
(u) They are malleable and ductile.

• Non-metals
(i) Non-metals are located at the top right hand side of the Periodic Table.
(ii) Non-metals are usually solids or gases at low temperature with low melting and
boiling points.
(iii) They are poor conductors of heat and electricity.
(iv) The non-metallic character increases as one goes from left to right across the
Periodic
Table.
(v) Most non-metallic solids are brittle and are neither malleable nor ductile.

• Metalloids
The elements (e.g., silicon, germanium, arsenic, antimony and tellurium) show the
characteristic, of both metals and non-metals. These elements are also called
semimetal.

• Noble Gases
– These are the elements present in group 18.
– Eash period ends with noble gas element.
– All the members are of gaseous nature and because of the presence of all the
occupied filled orbitals, they have very little tendency to take part in chemical
combination.
– These are also called inert gases.

• Representative Elements
The elements of group 1 (alkali metals), group 2 (alkaline earth metals) and group
13 to 17 constitute the representative elements. They are elements of s-block and p-
block.

• Transition Elements
The transition elements include, all the d-block elements and they are present in the
centre of the periodic table between s and p-block elements.

• Inner Transition Elements

Lanthanoids (the fourteen elements after Lanthanum) and actinides (the fourteen
elements after actinium) are called inner transition elements. They are also called f-
block elements.
The elements after uranium are also called transuranic elements.

• Periodic Trends in Properties of Elements

Trends in Physical Properties
Atomic Radii: It is defined as the distance from the centre of the nucleus to the
outermost shell containing the electrons. Depending upon whether an element is a
non-metal or a metal, three different types of atomic radii are used. These are:
(a) Covalent radius (b) Ionic Radius (c) van der Waals radius (d) Metallic radius.
(a) Covalent Radius: It is equal to half of the distance between the centres of the
nuclei of two atoms held together by a purely covalent single bond.
(b) Ionic Radius: It may be defined as the effictive distance from the nucleus of an
ion upto which it has an influence in the ionic bond.
(c) van der Waals Radius: Atoms of Noble gases are held together by weak van der
Waals forces of attraction. The van der Waals radius is half of the distance between
the centre of nuclei of atoms of noble gases.
(d) Metallic Radius: It is defined as half of the intemuclear distance between the two
adjacent metal ions in the metallic lattice.

• Variation of Atomic Radius in the Periodic Table

Variation in a Period: Along a period, the atomic radii of the elements generally
decreases from left to right.

Variation in a group: The atomic radii of the elements in every group of the periodic
table increases as we move downwards.
• Ionic Radius
The ionic radii can be estimated by measuring the distances between cations and
anions in ionic crystals.
In general, the ionic radii of elements exhibit the same trend as the atomic radii.

Cation: The removal of an electron from an atom results in the formation of a cation.
The radius of cation is always smaller than that of the atom.

Anion: Gain of an electron leads to an anion. The radius of the anion is always larger
than that ‘ of the atom.

Isoelectronic Species: Some atoms and ions which contain the same number of
electrons, we call them isoelectronic species. For example, O2-, F–, Na+ and Mg2+ have
the same number of electrons (10). Their radii would be different because of their
different nuclear charges.

• Ionization Enthalpy
It is the energy required to remove an electron from an isolated gaseous atom in its
ground state.
M (g) + I.E ——->M+ (g) + e–
The unit of ionization enthalpy is kJ mol-1 and the unit of ionization potential is
electron volt per atom.

Successive Ionization Enthalpies

If a gaseous atom is to lose more than one electron, they can be removed one after
the other i.e., in succession and not simultaneously. This is known as successive
ionization enthalpy (or potential).
• Variation of Ionization Enthalpies in the Periodic Table:

Variation of Ionization Enthalpy Along a Period

Along a period ionization enthalpies are expected to increase in moving across from
left to the right, because the nuclear charge increases and the atomic size decreases.

Variation of Ionization Ethalpy in a Group

The ionization enthalpies of the elements decrease on moving from top to the
bottom in any group.
The decrease in ionization enthalpies down any group is because of the following
factors.
(i) There is an increase in the number of the main energy shells (n) in moving from
one element to the other.
(ii) There is also an increase in the magnitude of the screening effect due to the
gradual increase in the number of inner electrons.

• Electron Gain Enthalpy

Electron Gain Enthalpy is the energy released when an electron is added to an
isolated gaseous atom so as to convert it into a negative ion. The process is
represented as:

For majority of the elements the electron gain enthalpy is negative. For example, the
electron gain enthalpy for halogens is highly negative because they can acquire the
nearest noble gas configuration by accepting an extra electron.
In contrast, noble gases have large positive electron gain enthalpies because the
extra electron has to be placed in the next higher principal quantum energy level
thereby producing highly unstable electronic configuration.

Successive Electron Gain Enthalpies

We have studied that electrons from a gaseous atoms are lost in succession (i.e., one
after the other). Similarly, these are also accepted one after the other, i.e., in
succession. After the addition of one electron, the atom becomes negatively charged
and the second electron is to be added to a negatively charged ion. But the addition
of second electron is opposed by electrostatic repulsion and hence the energy has to
be supplied for the addition of second electron. Thus the second electron gain
enthalpy of an element is positive.
For example, when an electron is added to oxygen atom to form O– ion, energy is
released. But when another electron is added to 0- ion to form O2- ion, energy is
absorbed to overcome the strong electrostatic repulsion between the negatively
charged 0– ion and the second electron being added. Thus, first electron gain
enthalpy:

Factors on which Electron Gain Enthalpy Depends

(i) Atomic size: As the size of an atom increases, the distance between its nucleus
and the incoming electron also increases and electron gain enthalpy becomes less
negative,
(ii) Nuclear charge: With the increase in nuclear charge, force of attraction
between the nucleus and the incoming electron increases and thus electron gain
enthalpy becomes more negative.
(iii) Symmetry of the Electronic Configuration: The atoms with symmetrical
configuration (having fully filled or half filled orbitals in the same sub-shell) do not
have any urge to take up extra electrons because their configuration will become
unstable.
In that case the energy will be needed and electron gain enthalpy (Δ eg H) will be
positive. For example, noble gas elements have positive electron gain enthalpies.
Variation of Electron Gain Enthalpy Across a Period
 Electron gain ethalpy becomes more negative with increase in the atomic number
across a period.
Variation of Electron Gain Enthalpy in a Group
Electron gain enthalpy becomes less negative as we go down a group.

• Electronegativity
A qualitative measure of the ability of an atom in a chemical compound to attract
shared electrons to itself is called electronegativity. Unlike ionization enthalpy and
electron gain enthalpy, it is not a measurable quantity.
However, a number of numerical scales of electronegativity of elements viz, Pauling
scale, Milliken- Jaffe scale, Allred Kochow scale have been developed. The
electronegativity of any given element is not constant; it varies depending on the
element to which it is bound.
Across a Period
Electronegativity generally increases across a period from left to right.
In a Group
It decreases down a group.

• Periodic Trends in Chemical Properties along a Period

(i) Metallic character: Decrease across a period maximum on the extreme left (alkali
metals).
(ii) Non-metallic character: Increasess along a period. (From left to right).
(iii) Basic nature of oxides: Decreases from left to right in a period.
(iv) Acidic nature of oxides: Increases from left to right in a period.

• Variation from Top to Bottom on Moving Down a Group

(i) Metallic character. Generally increases because increase in atomic size and hence
decrease in the ionizatiort energy of the elements in a group from top to bottom.
(ii) Non-metallic character. Generally decreases down a group. As electronegativity of
elements decreases from top to bottom in a group.
(iii) Basic nature of oxides. Since metallic character or electropositivity of elements
increases in going from top to bottom in a group basic nature of oxidise naturally increases.
(iv) Acidic character of oxides. Generally decreases as non-metallic character of elements
decreases in going from top to bottom in a group.
(v) Reactivity of metals. Generally increases down a group. Since tendency to lose electron
increases.
(vi) Reactivity of non-metals. Generally decreases down the group, Higher the electro-
negativity of non-metals, greater is their reactivity. Since electronegativity of non-metals in
a group decreases from top to bottom, their reactivity also decreases.

• Anomalous Properties of Second Period Elements

The first element of each of the group 1 (lithium) and 2 (beryllium) and group 13-17 (boron
to fluorine) differs in many respect from the other members of their respective groups. For
example, lithium unlike other alkali metals, and beryllium unlike other alkaline earth metals
form compounds which have significant covalent character; the other members of these
groups, pre-dominatly form ionic compounds.
It has been observed that some elements of the second period show similarities with the
elements of the third period placed diagonally to each other, though belonging to different
groups.
For example,

This similarity in properties of elements placed diagonally to each other is called diagonal
relationship.

• Mendeleev’s Periodic Law. Physical and chemical properties of elements are periodic
function of their atomic masses.
• Modem Periodic Law. Physical and chemical properties of the elements are periodic
function of their atomic numbers.
• Groups. There are 18 groups. These are vertical rows.
• Periods. There are 7 periods. These are horizontal rows.
• Representative Elements. The S and P block of elements are known as representative
elements.
• Transition Elements. They are also called d-block elements. They have general electronic
configuration (n – 1) d1-10 ns0-2.
• Inner Transition Elements. Lanthanoids (the fourteen elements after Lanthanum) and
actinides (the fourteen elements after actinium) are called inner transition elements.
General electronic configuration is (n – 2) f1-14(n – 1) d0-1 ns2.
They are also called f-block elements.
• Metals. Present on the left side of the periodic table. Comprise more than 78% of the
known elements.
• Non-metals. Mostly located on the right hand side of the periodic table.
• Metalloids. Elements which line as the border line between metals and non-metals (e.g.,
Si, Ge, As) are called metalloids or semimetals.
• Atomic Radii and Ionic Radii, increase down the group decrease along the period.
• Ionization Enthalpy. Increases along the period and decreases down the group.
• Noble Gas Elements. Elements with symmetrical configuration are chemically inert in
nature.
• Electric Nuclear Charge. Z = Nuclear charge – Screening constant.
• Electronegativity. Increases along a period decreases down the group,
• Chemical Reactivity. Chemical reactivity is highest at the two extremess of a period and
lowest in the centre.
• Oxides of Elements. Oxides formed of the Elements on the left are basic and of elements
on the right are acidic in nature.
Oxides of elements in the centre are amphoteric or neutral.
 3.Chemical Bonding
A chemical bond is that permits chemical compounds to develop connecting atoms, ions, or
molecules. Covalent bonds are produced by the sharing of electrons, whereas ionic bonds
are created by the electromagnetic force of difference in electronegativity.

Types of Chemical Bonds

1. Ionic Bond:-

The electrostatic interaction between positive and negative ions in a chemical molecule
forms an ionic bond, also known as an electrovalent bond. A bond is created when the
valence (outermost) electrons of one atom are irreversibly transferred to another atom.

Ionic bonds are formed by a cation and also an anion. The bond is formed when an atom,
often a metal, releases one or more electrons and transforms into a positive ion, or cation. A
non-metal atom can accept the electron(s) needed to create a negative ion, or anion.

Examples of Ionic Bond

i. LiF – Lithium Fluoride

ii. LiCl – Lithium Chloride
iii. LiBr – Lithium Bromide
iv. LiI – Lithium Iodide
v. NaF – Sodium Fluoride
vi. NaCl – Sodium Chloride
vii. NaBr – Sodium Bromide
viii. NaI – Sodium Iodide
ix. KF – Potassium Fluoride
x. KCl – Potassium Chloride

2. Covalent Bond:-
A chemical link involving the exchanging of electron pairs among atoms is known as a
covalent bond. Shared pairs or bonding pairs are the permanent balance of attractive and
repulsive forces between atoms when they share electrons, while covalent bonding is the
stable balance of attraction and repulsion between atoms when they share electrons.

When two or more atoms exchange one or maybe more pairs of electrons, they create a
covalent connection. At the same time, these particles are collected to both atomic nuclei.
When the difference in electronegativity of two or more elements is too tiny for an
electrostatic interaction to produce ions, a covalent bond is established.

a. Polar covalent bond:-

The electrons in a polar covalent bond are unequally shared by the atoms, and they spend
more time near to one than the other. Slightly positive (+) and slightly negative (–) charges
form in different sections of the molecule due to the uneven distribution of electrons
between both the atoms of different elements.

b. Non-Polar Covalent Bond:-

A nonpolar covalent link is a sort of chemical connection that occurs when two atoms share
electrons evenly. As a result, the number of electrons distributed by neighbouring atoms in
an atom would be the same. Because the electronegativity difference is usually minimal, the
covalent bond sometimes is referred to as nonpolar.
Covalent Bonding Types:-
Single Bond

In this case, atoms from the same or different elements hold a common electron to form
covalent bonds. Examples include CH4,H2, Cl2, and so on.

Double bond

In this case, atoms of the same or distinct elements share two electrons from each other to
form a double bond. Examples include C2H4,O2 CO2, and others.

Triple Bond

Each atom of the same and different elements shares three electrons in order to form three
covalent bonds between the two atoms associated in the covalent bond formation.
Examples include N2, C2H2, and others.

Covalent character of Ionic bond

The majority of covalent bonds have certain ionic character. Ionic bonds, too, have certain
covalent character. The origin of an ionic bond’s covalent character dwells in the distortion
of an electron cloud caused by an electric charge; this is known as polarizability, and the
process is known as polarisation. Polarising power is the ability of an electric charge to
reshape an electron cloud. The cations in an ionic compound as well as anions are
developed as a result of electron loss and gain respectively. As the cations are smaller, they
have greater polarising power and a higher charge density. Anions with larger sizes are
easily polarised. Anion’s electrons are less strongly connected to the nucleus than cations’.
The ionic bond can have a covalent character whenever the cation draws the electron cloud
of the anion, causing polarisation and the electron clouds to expand out towards the cation
that is present between the two ions.
 As a result, the electron lost by the cation does not fully correspond to the anion, but rather
returns to the cation and is shared by it.

Fajan suggested some empirical rules for dealing with polarisation. These are known
as Fajan’s rules, and they are as follows:

 The cations ought to be small in size.

 Anion of a large size.
 The presence of a cation with a high positive charge.

 Cations with electronic configuration (n-1) compared to cations with the same size and
charge but ns² np⁶ (noble gas) configuration.

The covalent character of an ionic bond is enhanced by the factors listed above.

Parameters of Covalent Bonds

Each covalent bond is defined by the following parameters, which are called as covalent
bond parameters:

Order of the Bond

The bond order of a molecule or ion is the number of bonds that exist between two atoms.
The bond order has a fixed value. Here are some examples:

 Order of bonds = 1

If there’s only one covalent bond or sigma bond among two bonded atoms, the bond order
is 1 (one). For example, H2, Cl2, and NH3.

Single bonds are another name for these.

Three single N-H bonds present in the NH3 molecule.

 Order of bonds = 2

When there are two covalent bonds among two bonded atoms, the bond order is 2 (two).

One sigma bond and one pi bond connect the bonded atoms. These are referred to as double
bonds.

 Order of Bond = 3
If there are three bonds among two bonded atoms, the bond order is 3 (three). One of these
bonds is a sigma bond, and the other two are pi bonds. These are known as triple bonds.

Length of Bond

Bond length is defined as the length between the nuclei of two bonded atoms. It is measured
in picometers (pm). The bond length is determined by the size of the bonded atoms and the
bond order of the bond that connects them. The bond length decreases as the bond order
increases.

Bonding Angle
The angle formed from two bonds in a molecule. Covalent bonds are formed by the orbitals
overlapping. The angle formed by two orbitals that contain bonding electrons and overlap
with other atoms’ atomic orbitals. The bond angle between two O-H bonds in an H2O
molecule is 104.5°, 107.3° between N-H bonds in an NH3 molecule, and 109°28 between C-
H bonds in CH4.

3. Coordinate bond:-

Coordinate Bond is a special type of covalent bond in which both electrons or an electron
pair that is shared between two atoms come from the same atom. Coordinate bonds are
also called Dative Bonds or Dipolar Bonds. Coordinate bonds are commonly found in
coordination compounds.

Characteristics of Coordinate Covalent Bond

Some chracterstics of Coordinate Covalent Bond are,
 Electron Pair Sharing: A coordinate bond is a type of covalent bond in which both
electrons in the bond come from the same atom.
 Donor and Acceptor: In coordinate bonding, one atom acts as the donor, sharing a
pair of electrons, and the other atom acts as the acceptor, receiving the shared
electron pair to attain a stable electronic configuration.
 Formation: Coordinate covalent bonds are usually formed in reactions that involve
two non-metals, such as a hydrogen atom, or during bond formation between metal
ions and ligands.
 Polarity: Coordinate bonds are always polar because they are formed between two
unlike atoms.
 Representation: In simple diagrams, a coordinate bond is shown by an arrow
pointing from the atom, donating the lone pair to the atom accepting it.
 Strength: Coordinate covalent bonds are usually strong, similar to other interatomic
bonds.

Types of Coordinate Bonds

Depending on the specific context and the atoms involved, these bonds can be considered
either weak or strong.
 Weak Coordinate Covalent Bonds: In some cases, coordinate covalent bonds can be
weaker than other covalent bonds due to the nature of the atoms involved or the
bonding arrangement. For example, coordinate covalent bonds formed between non-
metals or between a central electrophile and a ligand can be weaker than ionic bonds.
 Strong Coordinate Covalent Bonds: In other cases, coordinate covalent bonds can be
strong and have properties similar to other covalent bonds. For instance, coordinate
covalent bonds formed between transition metals or between two like atoms can be
strong.

Coordinate Bond in Ammonium Ion (NH4+)

Formation of ammonium ions involves a coordinate covalent bond. In this case, the
nitrogen atom in ammonia (NH3) donates its lone pair of electrons to the hydrogen ion
(H+). The nitrogen atom is the donor, and the hydrogen ion is the acceptor. The
coordinate covalent bond is represented by an arrow pointing from the nitrogen atom to
the hydrogen ion.

Properties of Coordinate Bond

The properties of a coordinate bond include:
 Directionality: A coordinate bond is a directional bond because the sharing of
electrons takes place in a specific direction.
 Isomerism: Some coordinate compounds exhibit isomerism, which is the existence of
two or more compounds with the same molecular formula but different structural
formulas.
 Melting and Boiling Points: Coordinate compounds generally have lower melting
and boiling points than ionic compounds.
 Strength: Since they involve the sharing of electron pairs, they are stronger than
hydrogen bonds but relatively weaker than ionic bonds.

Valence Bond Theory

VBT states that the overlap of incompletely filled atomic orbitals leads to the formation of a
chemical bond between two atoms. The unpaired electrons are shared and a hybrid orbital
is formed. VBT views bonds as weakly coupled orbitals (small overlap). When the orbitals
overlap along an axis containing the nuclei, they form a σ bond. VBT accounts for the
directional nature of covalent bonds.
What is Valence Bond Theory?
Valance Bond Theory also called VBT is the basic theory used to explain the structure and
the bonding in coordination compounds. This theory is used to explain the formation of the
bonds in the various atomic orbitals of the coordination compounds.
Valance bond theory assumes that the bonds are formed by individual atoms by the
donations of electrons. But this assumption is wrong as in reality the bonds in the
coordination bond are formed by the delocalization of the electrons in the orbitals of the
coordination compounds. Valance Bond Theory class 11 is the basic theory that helps us
visualize how various bonds are formed in nature.

What is Hybridization?
In the year 1931, scientist Linus Pauling proposed the innovative concept of hybridization.
He called the process hybridization and characterized it as the shifting of the energy of
particular atoms’ orbitals to produce new orbitals of equivalent energy. New orbitals,
known as hybrid orbitals, emerge as a result of this process. The hybrid orbitals are shown
in the image added below,

Various types of hybridization are:-

sp-Hybridization
One s and one p-orbital are combined together to generate two sp–hybrid orbitals with a
linear structure and a bond angle of 180 degrees. For example, when BeCl2 is formed, the
first atom is in the excited state 2s1 2p1, which is then hybridized to generate two sp–
hybrid orbitals. BeCl2 is formed when these hybrid orbitals collide with the two p-orbitals
of two chlorine atoms.

sp2–Hybridization
One s and one p-orbital are combined together to generate three sp2– hybrid orbitals with a
planar triangular shape and a bond angle of 120 degrees.
sp3-Hybridization
One s and three p-orbitals are merged in this hybridization to generate four sp3– hybrid
orbitals with a tetrahedral structure and a bond angle of 109 degrees 28′, or 109.5 degrees.

Number of Orbitals and Types of Hybridization

VBT explains that we have (n-1)d, ns, np, or ns, np, nd that are used for hybridization and
they form hybrid orbital in which the electrons then reside. The various types of hybrid
orbitals are responsible for various shapes that are shown in the table below,
Coordination Number Types of Hybridisation Shape of Hybrid Orbital

4 sp3 Tetrahedral

4 dsp2 Square Planar

5 sp3d Trigonal Bipyramidal

6 sp3d2 Octahedral

6 d2sp3 Octahedral

What is Need for Valence Bond Theory?

Lewis’ theory explained the structure of molecules. It did not, however, explain the
formation of chemical bonds. VSEPR theory, on the other hand, explained the shape of
simple molecules. However, it had a very limited application. It also failed to explain the
geometrical properties of complex molecules. As a result, scientists were forced to develop
the theory of valence bonds in order to address and overcome these limitations.

Postulates of Valence Bond Theory

Various postulates of VBT or Valance Bond Theory are,
 When two or more valance orbitals (half-filled) overlap each other they formed
balanced orbital and then the electrons are filled in those orbitals accordingly.
 Only unpaired electrons of the orbital participate in the filling of valance orbital. Paired
electrons do not participate in the filling of valance orbital.
 Covalent chemical bond formed by the valance atomic orbital are directional in nature.
 Valance Bond formed are Sigma Bond and Pi Bond, if orbitals overlap head to head they
form Sigma Bond, if the orbital overlap sidewise they form Pi bond.

Applications of Valence Bond Theory

 Valence Bond Theory explain the formation of covalent bond in various compounds.
 The strength of various bonds of the compounds are explained by Valance Bond Theory
(VBT), i.e. the strength of H2 and F2 are explain using Valance Bond Theory.

Limitations of Valence Bond Theory

The limitations of the Valance Bond Theory are,
 Tetravalency of the carbon atom is not explained by the Valance Bond Theory (VBT)
 Strong Ligand and Weak Ligand are not differentiate using Valance Bond Theory (VBT)
 The localization of electrons are not explained using valance Bond Theory (VBT)
 This theory fails to explain the colour exhibited by the coordination compounds.

Valence Bond Theory Examples

Valence bond theory (VBT) is used to explain how covalent bonds form in many
compounds. Here are some examples of VBT:
 Water (H2O): Water is made up of two hydrogen atoms bound to an oxygen atom. Each
hydrogen atom has an s-orbital with one lone electron, and oxygen has an s-orbital with
an electron pair.
 Fluorine Molecule (F2): The F-F bond in the diatomic fluorine molecule is formed by
the intersection of the two F atoms’ pz orbitals, each of which contains an unpaired
electron.
 Ethylene (C2H4): Both C atoms have three bonding pairs and no lone pairs, meaning
they are both sp2 hybridized.
 Methylamine (CH3NH2): Both the carbon and the nitrogen atom are sp3-hybridized.
The C-N sigma bond is an overlap between two sp3 orbitals

VBT can also explain the difference in the length and strength of the chemical bonds in H2
and F2 molecules.

Intermolecular forces:-

Intermolecular forces are the electrostatic interactions between molecules. The intermolecular
forces are usually much weaker than the intramolecular forces, but still, they play important
role in determining the properties of the compounds. The major intermolecular forces include
dipole-dipole interaction, hydrogen bonding, and London dispersion forces.

Dipole-dipole interactions:-

Polar molecules have permanent dipoles, one end of the molecule is partial positive (δ+) and the
other is partial negative (δ-). The polar molecules have electrostatic interactions with each
other through their δ+ and δ- ends called dipole-dipole interactions, though these interactions
are weaker than ionic bonds. The polar molecules orient in a way to maximize the attractive
forces between the opposite charges and minimize the repulsive forces between the same
charges

Illustration of dipole-dipole interactions by dotted liens in polar molecules.

London dispersion forces:-

It may appear that the nonpolar molecules should not have intermolecular interactions.
Practically, there are intermolecular interactions called London dispersion forces, in all the
molecules, including the nonpolar molecules. The electron cloud around atoms is not all the
time symmetrical around the nuclei. It temporarily sways to one side or the other,
generating a transient dipole. The transient dipole induces a dipole in the neighboring. A
transient dipole-induced dipole interaction, called London dispersion force or wander
Wall’s force, is established between the neighboring molecules Although London
dispersion forces are transient, they keep re-appearing randomly distributed in space and
time. London dispersion forces are not unique to nonpolar molecules, they are present in all
types of molecules, but these are the only intramolecular forces present in the nonpolar
molecules.

Illustration of transient dipole-induced dipole, i.e., London dispersion forces.

4.Gaseous State
Ideal Gas

An Ideal Gas is a theoretical representation of a gas that is composed of point particles that do
not show any changes during intermolecular movements. This gas represents all the 3 primary
laws as stated by Boyle, Charles, Gay Lussac and Avogadro

Hence,

From Boyle’ law – V ∝ 1/P where T and n are constant

From Charle’s Law – V ∝ T where P and n are constant

Finally, from Avogadro’s Law – V ∝ n where T and n are constant

Thus combining all will give us V ∝ n X T/P

Therefore, mathematically we can express it as:

PV = nRT

Where,

P stands for pressure

V stands for Volume

T stands for temperature

R stands for Ideal Gas Constant

&

n stands for the amount of substance

An Ideal gas equation occurs when all the 3 laws can be combined together in a single
equation. It is referred to as the relation between four variables and it describes the state of
any gas, therefore, it is also called the equation of state.
Ideal Gas Equation

The ideal gas equation is a combination of all the individual gas laws. Boyle’s Law, Charle’s law,
Gay-Lussac’s Law and Avogadro’s Laws are the basis of the Ideal gas equation.

After the analysis of the experiments in various gas laws, we can understand the idea behind
the ideal behaviour of gases. The ideal gases perfectly obey the Ideal Gas Laws. The law of Ideal
gases states that the volume of a specified amount of gas is inversely proportional to pressure
and directly proportional to volume and temperature. Before deriving the Ideal Gas Law lets
revise what various Gas Laws say.

Boyle’s Law

It states that at a constant temperature, the volume of a gas is indirectly proportional to

pressure. This implies that with an increase in pressure the volume of the gas will decrease.
Mathematically Boyle’s law is summarized as V ∝ 1/P

Charle’s Law

According to the Charle’s Law, at constant pressure, the volume of a gas is directly
proportional to temperature. This means that with increasing temperature, the volume of the
gas increases. Mathematically Charle’s Law can be written as V ∝ T

Avogadro’s Law

Avogadro’s law states that at standard temperature and pressure conditions, the volume of a
gas is directly proportional to the number of molecules of the gas. Therefore, mathematically
we write it as V ∝ n

The Equation

Now putting all the three laws together, we find that at standard conditions, Volume of a gas
can be represented as follows:

V ∝ T × n × 1/P
V = R × T × n × (1/P)
R, here is a proportionality constant. Therefore we can write, P V = n R T or R = PV/nT. Also
called as the Gas Constant, R is same for all gases. This is therefore also called Universal Gas
Constant. From the analysis of the three Gas laws, we get the Ideal Gas Equation:

PV=nRT

Therefore if the number of moles (n) is 1 we get pV= RT. Now taking the value of m/M for n we
write: pV=(m/M) RT ; (n=m/M)

Since pV= mRT /M = (mRT)/VM

Therefore, p = (dRT)/M (Since, d =m/V)

Hence we have: d = (pM) /RT

M= dRT/P. This equation brings us to the conclusion that under unchanged conditions of
temperature, and pressure the density of a gas is directly proportional to the molar mass of the
gas.

Kinetic Theory of Gases: Gas Law

For our earlier discussion, we had understood that gas quantities like Temperature,
Pressure, Volume and mass are interconnected with each other. And the law that
interconnects this quantity is known as Gas laws, these gas laws are given as

1. Boyle’s Law
2. Charles’ Law
3. Gay Lussac’s Law

Let’s go through it one by one.

Kinetic Theory of Gases: Boyle’s Law

According to Boyle’s Law, the Volume of any given mass of gas is inversely proportional to
its pressure as long as the temperature is kept constant

i.e., PV= constant

P1V1=P2V2P1V1=P2V2 = constant

Where,

PiPi = Pressure of given mass of gas at some instance i

ViVi = Volume occupied by gas at some instance i

 Fig – Experimental P-V curves (solid lines) for steam at three temperatures compared with Boyle’s Law
(dotted lines). P is in units of 22 atm and V in units of 0.09 litres.

The given graph is just to show how Pressure vs Volume curve varies for a system of gas at
three different temperature (T1),(T2),(T3)(T1),(T2),(T3), here temperature will be
constant for any given instant 1, 2 and 3

We can rewrite the law in form of Root Mean Square Velocity as

P=13ρC2RMSP=13ρCRMS2

P=13mNVC2RMSP=13mNVCRMS2

PV=13mNC2RMSPV=13mNCRMS2

∴13mNC2RMS=constant∴13mNCRMS2=constant

Kinetic Theory of Gases: Charles’ Law

According to Charles’ law, the volume (V) of given mass of gas will be directly proportional
to its temperature (T) at that given instant as long as the system is at constant pressure

V∝T orV1T1=V2T2=constantV∝T orV1T1=V2T2=constant

Fig – Experimental T-V curves (solid lines) for CO2 at three pressures compared with Charles’ law (dotted lines). T is
in units of 300 K and V in units of 0.13 litres.
The given graph is just to show how the Temperature vs Volume curve varies for a system
of gas for three different pressures (P1),(P2),(P3)(P1),(P2),(P3), here temperature will be
constant for any given instant 1, 2 and 3.

Kinetic Theory of Gases: Pressure Law or Gay Lussac’s Law

According to Gay Lussac’s Law or Pressure Law, at some constant volume (V) both pressure
and temperature will be directly proportional to each other.

P∝T orP1T1=P2T2=constant

Deviation of Real Gases from Ideal Gas Behaviour

A state of matter is one of the different forms. In everyday life, four states of matter are
visible: solid, liquid, gas, and plasma. Many intermediate states, such as liquid crystal, are
known to exist, and certain states, such as Bose-Einstein condensates, neutron-degenerate
matter, and quark-gluon plasma, are known to exist only under severe conditions, such as
extreme cold, extreme density, and extreme energy. See the list of states of matter for a
complete list of all exotic states of matter.

Behaviour of Real Gases

All of the gases are real-life instances. Although there is no such thing as an ideal gas, genuine
gases are known to behave in ideal ways under certain circumstances. Nitrogen, oxygen,
hydrogen, carbon dioxide, helium, and other actual gases are examples.
Ideal Gas and Real Gas: An ideal gas obeys the ideal gas equation PV=nRT at all pressures
and temperatures. No gas, on the other hand, is excellent. Almost all gases vary in some
manner from the ideal behaviour. Non-ideal or actual gases, such as H2, N2, and CO2, do not
obey the ideal-gas equation.

Compressibility Factor

A new function called the Compressibility factor, denoted by Z, can be used to quantify the
degree to which real gas deviates from ideal behaviour. It’s described as
Z = PV/RT
Plotting the compressibility factor, Z, vs. P, reveals the degree of departure from optimum
behaviour. Temperature and pressure have no effect on an ideal gas, which has a Z value of
1. The value of Z is more or less than 1 determines the difference between ideal and real gas
behaviour. The degree of gas nonideality is represented by the difference between unity
and Z. Pressure and temperature cause deviations from optimal behaviour in a real gas.
Using pressure and temperature to examine the compressibility curves of some of the gases
discussed below.

Effect of Pressure Variation on Deviations

In the graph below, the compressibility factor, Z, for H2, N2, and CO2 at constant temperature
is plotted against pressure.
For all of these gases, Z is practically equal to one at very low pressure. Real gases behave
almost perfectly at low pressures (up to 10 atm). As the pressure rises, H2 exhibits a steady
increase in Z (from Z=1). As a result, the H2 curve is higher than the ideal gas curve at all
pressures. For N2 and CO2, Z decreases at first (Z1), then reaches a minimum, and finally
increases with increasing pressure (Z>1). Because CO2 is the most easily liquefied gas, it has
the greatest drop in the curve.

Effect of Temperature on Deviations

The graph below shows plots of Z or PV/RT against P for N2 at various temperatures.

As the temperature rises, the deviations from ideal gas behaviour become smaller and
smaller, as shown by the shape of the graphs. At lower temperatures, the curve dips
significantly, and the slope of the curve is negative. In this situation, Z<1. As the
temperature rises, the dip in the curve decreases. The curve’s minimum vanishes at a
certain temperature and remains horizontal for a wide range of pressures. At this
temperature, PV/RT is nearly equal, thus Boyle’s law is satisfied. As a result, Boyle’s
temperature refers to the temperature of the gas. Each gas has its own Boyle temperature,
such as 332K for N2.
Note:
1. Real gases perform approximately ideal at low pressures and relatively high temperatures,
and the ideal-gas equation is obeyed.
2. A real gas deviates greatly from ideality at low temperatures and sufficiently high
pressures, and the ideal-gas equation is no longer valid.
3. As the gas approaches the liquefaction point, the departure from ideal behaviour grows.

Van der Waals Equation (Causes of Real Gas Behaviour)

The Van der Waals equation is an equation of state that describes the behavior of real gases,
taking into account the volume of the gas molecules and the attractive and repulsive forces
between them. The equation is named after Dutch physicist Johannes Diderik van der
Waals, who proposed it in 1873.
The Van der Waals equation is:
(P + a(n/V)^2)(V – nb) = nRT

where P is the pressure, V is the volume, n is the number of moles of gas, R is the gas
constant, T is the temperature, a is a measure of the attractive forces between gas
molecules, and b is a measure of the volume of the gas molecules.
The Van der Waals equation is based on two assumptions about real gases:
Volume of gas molecules: In real gases, the volume of the gas molecules is not negligible
compared to the volume of the container in which the gas is held. This means that the actual
volume occupied by the gas is slightly less than the volume of the container.
Intermolecular forces: In real gases, there are attractive and repulsive forces between gas
molecules, which affect the behavior of the gas. The attractive forces between gas molecules
cause the gas molecules to be attracted to each other, which reduces the pressure of the gas.
The repulsive forces between gas molecules cause the gas molecules to repel each other,
which increases the pressure of the gas.
The Van der Waals equation takes these factors into account and provides a more accurate
description of the behavior of real gases, particularly at high pressures and low
temperatures, where the ideal gas law breaks down.
Volume Correction
The volume of a gas is the amount of free space in the container where molecules can move
about. The volume V of an ideal gas is equal to the volume of the container. Because ideal
gas molecules have no volume, they can freely move around inside the container. In
contrast, Van der Waals thought of molecules in a genuine gas as rigid spherical objects with
a fixed volume.

As a result, the volume of a real gas is ideal volume minus gas molecule volume. If b is the
effective volume of molecules per mole of gas, the volume of the ideal gas equation is
rectified as follows:
It becomes, (V–b) for n moles of gas.
(V–nb)
Where,
The excluded volume, abbreviated as b, is a constant and unique quantity for each gas.
Pressure Correction
A molecule in the interior of gas is attracted by molecules on all sides. These appealing
characteristics cancel each other out. A molecule poised to impact the vessel’s wall, on the
other hand, is drawn only by molecules on one side. It feels forced to go inside as a result. As
a result, it hits the wall with less force, and the real gas pressure, P, is less than the ideal
pressure. If the actual pressure P is smaller than the ideal pressure Pideal by a factor p, we’ve
got
P = Pideal – p
Pideal = P + p

Van der Waals determined the value of quantity p as follows:

p = an2/V2
Where n is the total number of gas molecules in volume V, and a denotes the gas’s
proportionality constant. As a result, the ideal gas equation’s pressure P is revised to:
For n moles of gas, use (P+an2/V2).
When the adjusted pressure and volume numbers are substituted in the ideal gas equation,
PV=nRT, we get:
(p+an2/V2) (V–nb) = nRT
For n moles of a gas, this is known as the Van der Waals equation or real gas equation. The
Van der Waals equation becomes: for 1 mole of gas (n=1):
(p+a/V2)(V–b) = RT

Van Der Waals Equation:-

The Van der Waals equation of state is another name for the Van der Waals equation. The
connection between the pressure, volume, temperature, and quantity of actual gases is
depicted by the Van der Waals equation. This equation was created in 1873 by Johannes
Van der Waals. This new equation is an extension of the ideal gas law, which also discusses
how molecules in a gas interact with one another and have finite sizes. The Van der Waals
equation is acceptable to both ideal gases and real gases, whereas the ideal gas law only
applies to ideal gases. This is the main distinction between the two.

The following is the Van der Waals equation:

(P+an2V2)(V−nb)=nRT(P+an2V2)(V−nb)=nRT
Where,

P= pressure

V= volume

a= constant that measures the attractive force between the molecules

b= volume correction factor

nb= volume occupied by the gas molecules

T= Temperature

Derivation:-

What is Van Der Waals Equation?

The Van der Waals equation of state is another name for the Van der Waals equation. The
connection between the pressure, volume, temperature, and quantity of actual gases is
depicted by the Van der Waals equation. This equation was created in 1873 by Johannes
Van der Waals. This new equation is an extension of the ideal gas law, which also discusses
how molecules in a gas interact with one another and have finite sizes. The Van der Waals
equation is acceptable to both ideal gases and real gases, whereas the ideal gas law only
applies to ideal gases. This is the main distinction between the two.
The following is the Van der Waals equation:

(P+an2V2)(V−nb)=nRT(P+an2V2)(V−nb)=nRT

Where,

P= pressure

V= volume

a= constant that measures the attractive force between the molecules

b= volume correction factor

nb= volume occupied by the gas molecules

T= Temperature

Units of Van der Waals Constants

The Van der Waals equation of state includes two constants, 'a' and 'b', which are known as
the Van der Waals constants.
Unit of Van der Waals constant a is atm lit² mol⁻².
Unit of Van der Waals constant b is litre mol⁻¹.

Volume Correction in Van der Waals Equation

The 'nb' term in the equation represents the volume correction. The term 'n' multiplied by
'b' accounts for the volume occupied by the gas molecules themselves. This correction
adjusts the available volume by subtracting the volume occupied by the molecules, leading
to a reduction in the overall volume available for the gas to expand.

By using this correction term, the Van der Waals equation provides a better estimation of
real gas behavior, especially when compared to the ideal gas law, which assumes negligible
molecular volume and no intermolecular interactions.

Pressure Correction in Van der Waals Equation

The an2V2an2V2 term in the Van der Waals equation represents the pressure correction.
The term 'n/V' represents the molar density of the gas, and 'a' is a constant that accounts
for the strength of the intermolecular attractive forces. The correction
term an2V2an2V2 adds an extra term to the pressure to consider the decrease in pressure
due to attractive forces between the gas molecules.

The attractive forces between gas molecules reduce the pressure exerted by the gas, and
incorporating the 'a(n/V)^2' term in the Van der Waals equation provides a more accurate
prediction of real gas behavior compared to the ideal gas law, which assumes no
intermolecular forces.
Derivation of Van Der Waals Equation for Real Gases

The Van der Waals equation is derived from the Kinetic Theory of Gases by correcting the
pressure and volume of the ideal gases. The ideal gas law state that PV = nRT, where n is the
number of moles, P is the pressure, V is the volume, T is the temperature, and R is the
constant of all gases. It is also referred to as the Van der Waals equation of state for real
gases that do not adhere to the ideal gas law.

o The gas molecules do not interact with one another through an attractive force.
Therefore, a correction to the pressure (P+aV2P+aV2) is necessary.
o When compared to the gas molecule’s overall volume, the volume the gas molecule
acquires is insignificant. So, the Volume should be corrected ( V-nb).

So, Let’s put values in the Ideal gas equation, PV=nRT

Thus,

(P+aV2)(V−nb)=nRT(P+aV2)(V−nb)=nRT

Derivation of Van Der Waals Equation for one Moles of Gas

Let the one mole of gas consist only of particles that don’t interact. According to the ideal
gas equation’s law,

PV = nRT

In this case, V will be replaced by the co volume ‘b’ (V – b), where b is known as the
excluded volume or co volume. Consider the effect of the limited volume of the particulate
to decrease the usable space in which the particles are available that can be free for
movement.

Thus, the equation becomes, P(Vm−b)=RTP(Vm−b)=RT

Let’s now think about the forces that pull particles together. Van der Waals assumed that:

The total net force that pulls the molecule into the container and acts on its surface area is
directly proportional to the density distribution given by,

C=NaVmC=NaVm

Additionally, the pressure is decreased by a factor related to the square of the density, and
the force between the walls is reduced by a factor

a′C2= a′(NaVm)2=aVm2a′C2= a′(NaVm)2=aVm2

Thus, the net pressure is

P=(RTVm−b)(a2V2m)P=(RTVm−b)(a2V2m)

The equation will produce the second form of the formula given above after writing n for
the number of moles and nVm equal to V.
(P+an2V2)(V−nb)=nRT(P+an2V2)(V−nb)=nRT

Van der Waals Equation Applied to Compressible Fluids

Compressible fluids like Polymers can be written as,

(p+A) (V-B) = CT – equation (1)

Where,

p: pressure applied on the fluids

V: specific volume of the fluid

T: temperature of the fluid

A, B and C are parameters of the fluid

Hence, equation (1) is the Van der Waals equation applied to compressible fluids.

Advantages and Disadvantages of Van Der Waals Equation

The following are few advantages and disadvantages of Van Der Waals Equation:

Advantages

o In comparison to the ideal gas equation, it aids in precisely predicting the behaviour
of gas.
o Although there are gases in this equation, fluids can also use them.

Disadvantages

o Only real gases that are above the critical temperature can accurately be determined
using this equation.
o The results can also be accepted for gases below the critical temperature.
o The equation fails when the gas is in its transitional phase.
 5.Solutions
The solution is a homogeneous mixture of 2 or various substances in the same and
different physical phases. The substances forming the solution are known as
components of the Solution. A solution of two components is called a binary solution
based on the number of components. Under this section of class 12 Chemistry chapter 2
notes, we will focus on liquid solutions and their various properties in this unit.

Solute and Solvent

In a binary solution, the solvent is the component present in large quantities, while the
other component is known as Solute. For Example, salt solution.

 Solution: It is a mixture of two or more components that is homogeneous—for

Example, ordinary salt in water.
 Solute: The component present in a lesser amount or whose physical state is changed
during the formation of the Solution is called Solute.
 Solvent: The component present in more significant amounts and determines the
physical state of the Solution is called a solvent.

Solutions can be broadly categorised in 2 ways:

 Homogeneous solutions: Solutions with the same composition and properties

throughout the Solution are homogeneous solutions. E.g. Solution of NaCl (salt) or sugar
in water, cough syrup, a cup of coffee, Mouthwash, perfume is a homogeneous mixture
of chemicals and dyes, etc.
 Heterogeneous solutions: Solutions with not the same composition and properties
throughout the Solution are heterogeneous solutions. E.g., solution of oil and water,
water and sand, water and chalk powder, etc.

Classification of Solutions

Types of Solute Solvent Examples

Solution

Solid solid Solid Alloys

solutions

Liquid Solid Mercury and Amalgam

Gas Solid Dissolve gases in

minerals

Liquid Solid Liquid Glucose that has been

 solutions dissolved in water

Liquid Liquid Ethanol is a liquid that

can be dissolved in
water.

Gas Liquid Water with oxygen

dissolved in it

Gas solutions solid Gas Iodine vapour in the air

Liquid Gas Water vapour in the air

Gas Gas Air (combination of

nitrogen and oxygen)

If H2O is used as a solvent, the solution is known as an aqueous solution, and if not, the
solution is called a non-aqueous solution. Apart from the class 12 Chemistry chapter 2
notes, students may also refer to NCERT books for more information.

Expressing Concentration Of Solutions

Under this section of class 12 Chemistry chapter 2 notes, students learn about the
concentration of solutions. The solution concentration refers to the amount of Solute
dissolved per unit of solution.

 The strength of a solution is the measure of the composition of a solution.

 A solution with a relatively massive quantity of Solute is called a concentrated solution.
 A solution with a relatively minimal quantity of Solute is called a dilute solution.

There are various methods for determining the strength of a solution which are as
follows.

1. Mass Percentage (%w/w): “It represents the mass of a component in

100 g of Solution.

Mass % of a component = Mass of the component in the solution X 100

The total mass of solutions

For Example Mass percentage of glucose in a 100g solution containing 10 g of glucose

dissolved in 90 g of water is 10%.

Mass % of glucose= Mass of glucose in the solution x 100

The total mass of the Solution

=10/100×100 = 10 %

The second Example of Commercial bleaching solution contains a 3.62 mass percentage
of sodium hypochlorite in water.

2. Volume Percentage (%v/v): As represented in class 12 Chemistry

chapter 2 notes, Volume percentage can be defined as “Represents the
volume of a component in a solution of 100 mL.

Volume % of a component = Volume of component X 100

Total volume of solution

For Example, a 35.5 % (v/v) solution of ethylene glycol, an antifreeze, is utilised in cars
and buses for cooling the engine. At this concentration, the antifreeze reduces the
freezing point of H2O to 255.4K or –17.6°C.

3. Mass by Volume Percentage %( w / v): “It represents the mass of the

solute in grams dissolved in 100 mL of solutions.”

Mass by volume % = Mass of Solute in g X 100

The volume of Solution in mL

For Example, Rashida dissolved 40g of sugar in 600 mL of sugar solution. Calculate the
mass by volume percentage.

Solution : Mass by volume% =Mass of volume/Volume of solutions x 100 = 40g/600 x

100 = 6.66%

4. Parts Per Million (ppm): It can be defined as the ratio of several parts to
the total number of elements of each component of the solution
multiplied by 106. It shows the concentration of a solution where Solute
is present in the trace. For instance, the concentration of pollutants in
water or the atmosphere is often described in terms of g mL–1 or ppm.

Mathematically,

Parts per million = No. of parts of the component X 106

The total number of all the components of sol.

For example, let 0.0005g of sodium chloride dissolved in 100mL of water then parts per
million =

= 0.0005/100 x 106= 0.000005 x 106 = 5 ppm

Volume to volume, Mass to mass, and mass to the volume are all ways to express
concentration in parts per million. Students may refer to class 12 Chemistry chapter 2
notes for more information.

5. Mole Fraction (x): As per Chemistry chapter 2 class 12 notes, “It

represents the number of moles of a solute in one mole of solution.”

Mole fraction = No. of moles of the component

Total no. of moles all the component

If the amount of moles A and B in the binary mixture is nA and nB, respectively, the
mole fraction of A will be

xA = nA

_____________

nA + nB

6. Molarity, M: It denotes the number of moles of Solute in 1 litre of

Solution.

Molarity, M = Moles of Solute

Vol. of sol in L

Molarity is measured in milligrams per litre and is expressed by the letters ‘M ‘or
‘Molar.’ “The density of a solution is its mass per unit volume.”

Density = Mass of Solution

Vol. of Solution

Students may refer to class 12 Chemistry chapter 2 notes provided by Extramarks to get
a clear understanding of Molarity. In addition, students may also refer to study notes,
essential questions, and sample question papers specific to Solutions – chapter 2
Chemistry class 12 notes.

7. Molality, m: It represents the number of moles of solute present per

kilogram of solvent

Molality, m = Moles of Solute

Mass of solvent in kg

Molality is calculated in mol/kg, which can also be expressed as ‘m’ or ‘molal.’

 For instance, the molality of a solution containing 74.5 g (1 mol) of potassium chloride
dissolved in one kg of water is 1.00 m or 1.00 mol kg–1.

8. Normality, N: It represents the number of solute equivalents in 1 litre of

Solution.

Normality, N = No. of Equivalents of Solute

Vol. of sol. in L

No. of equivalents, eq = Weight_____

Equivalent weight(W/E)

E = M, where Z is the valency factor.

9. Formality: Ionic solutes do not exist in the form of molecules. This

molecular mass is expressed as Gram formula mass. Molarity for ionic
compounds is called formality.

Solubility

As defined under the class 12 Chemistry chapter 2 notes, Solubility is a physical

property of a solution. The solubility of a substance is its maximum amount that can be
dissolved in a specified amount of solvent.

Solubility property of Solution depends upon the factors like

 Nature of solute and solvent and interaction between them: The strong attraction
between solute and solvent molecules, the maximum will be the solubility.
 The molecular size of Solute: Larger molecules are more difficult to dissolve in
solvents, whereas the smaller molecules dissolve quickly and are more soluble.
 Polarity: Polar solvents (having bonds with different electronegativities) like Water,
ethanol, and formaldehyde dissolve polar solutes, whereas nonpolar solvents (having
bonds with similar electronegativities) like pyridine, toluene, and hexane dissolve
nonpolar solutes.
 Temperature: Rise in temperature increases the solubility.
 Pressure: Rise in pressure increases solubility.

Solubility of a Solid in Liquid

The solution of sugar or salt dissolved is a typical example of the solubility of a solid in a
liquid. But not all solids need to dissolve in liquid. For Example, solids like naphthalene
and anthracene do not mix in water but dissolve readily in benzene, but sugar and salt
do not dissolve in benzene. This is because it is a property of Solution that polar solutes
dissolve in polar solvents like water, ethanol, formaldehyde and chloroform, whereas
nonpolar solutes in nonpolar solvents like toluene, pyridine, as well as hexane.
 Some vital concepts as defined in class 12 Chemistry chapter 2 notes include

 The phenomenon of an increase in the concentration of Solution due to the dissolving of

solid solute to the solvent is called dissolution.
 The process of collision of solute particles in a solution resulting in the separation of the
solute particles from the solution is called crystallisation.
 A phase when the number of solute particles going into the solution is equal to the
solute particles separating from the solution is called equilibrium. The strength of the
solute remains the same at this phase.
 A solution in which no more solute can be dissolved into the solvent at
 constant pressure and temperature are called a Saturated solution.
 According to Le Chatelier’s Principle in a saturated solution, if the dissolution process is
endothermic (Δsol H > 0), the solubility should increase with a temperature rise. Still, if
the dissolution process is exothermic (Δsol H > 0), the solubility should decrease.
 Pressure does not have a crucial effect on the solubility of solids in liquids because they
remain unaffected by pressure due to the high incompressibility of solids and liquids.

Solubility of a gas in a liquid:

Aerated drinks and dissolved oxygen in water bodies that support aquatic life are
natural instances of solubility of a gas in a liquid. HCl is also highly soluble in water. The
phenomenon of an increase in the concentration of solution due to the dissolving of
solid solute to the solvent is called dissolution.

Dissolution of salt in water: The process of collision of solute particles in a solution

resulting in the separation of the solute particles from the solution is called
crystallisation. An example includes the Crystal of copper sulphate obtained by the
crystallisation of Copper Sulphate solution.

 A phase when the number of solute particles going into the solution is equal to the
number of solute particles separating from the solution is called equilibrium. The
strength of the solute remains constant at this stage of dynamic equilibrium.
 The solubility of a gas in a liquid is highly affected by temperature and pressure.
 An increase in temperature reduces the solubility of gases in liquids because in
dissolving gas molecules in a liquid, dissolution is similar to condensation leading to the
evolution of heat. Hence, dissolution is an exothermic process, due to which the
solubility decreases with an increase in temperature.
 An increase in pressure by compressing the gas to a minor volume increase the number
of
 gaseous particles per unit volume above the solution and the rate at which the gaseous
particles are striking the solution’s surface to enter it, leading to the increase in the
solubility of gases.

Henry’s Law

Henry’s Law establishes a quantitative relation between pressure and solubility of a gas
in a solvent. This Law is for gas-liquid Solutions. The solubility of a gas in a liquid is
directly proportional to the pressure of the gas at a fixed temperature, according to
Henry’s Law.
 As defined in class 12 Chemistry chapter 2 notes, “The partial pressure of the gas in the
vapour phase (p) is proportional to the mole fraction of the gas (x) in the solution,”
according to the most frequent version of Henry’s Law.

This is written as:

p = KH x

Here KH is the henry law constant.

At the constant temperature, different gasses have different KH. It is a role of the nature
of the gas. At a given pressure increasing the value of KH implies lower solubility of the
gas in the liquid. The value of KH increases with the increase in temperature; Hence
solubility of gases increases with decreasing temperature. Because of this reason, cold
water is more sustainable for aquatic life than warm water.

Henry’s Law has a Variety of Applications, as mentioned below.

 Sealing soft drink bottles at high pressure increases the solubility of CO2 in soft drinks
and soda water.
 When a diver goes underwater, his body is subjected to high pressure. Due to this, the
body tissues absorb more gases. The breathed-in oxygen is required for cellular
respiration to provide energy to the diver. But the nitrogen gets absorbed into the body
tissues.
 The pressure increases with the increase in depth. Therefore as the diver approaches
the bottom of the water body, the pressure increases. With this increase in pressure,
more nitrogen gets absorbed by the body tissues.
 They are challenging and can even cause a threat to their life. The water utilised by
scuba jumpers is loaded with contaminated air containing 11.7% helium, 56.2%
nitrogen, and 32.1% oxygen to protect the divers from such a situation.
 At high heights, the fractional weight of oxygen is not as much as that at the ground
level. This stimulates low oxygen concentrations in the blood and tissues of individuals
living at high heights or climbers. Low blood oxygen causes climbers to feel feeble and
not able to think plainly, indications of a condition known as anoxia.

Henry’s Law as a Specific Example of Raoult’s Law

With reference to class 12 Chemistry chapter 2 notes, Raoult’s Law builds a quantitative
relationship between the partial vapour pressure and the mole fraction of a solution.
This Law is only for liquid-liquid solutions. The Law states that for a solution of volatile
liquids, the partial vapour pressure (p) of each component in the solution is directly
proportional to its mole fraction (x). As a result, Raoult’s Law becomes a specific case of
Henry’s Law, in which

Mathematically, p ∝ x

Or p = p 0x

Where p0 is the vapour pressure of a pure component at the constant temperature.

Hence, for component 1, p1 = p1 0 x1 and for component 2 p2 = p20 x

Let the solvent be represented by one and solute be represented by 2. At this point, if
the solute is non-volatile, just the solvent molecules are present in the vapour phase and
add to vapour pressure.

so p1 = vapour pressure of the solvent,

x1 = mole fraction,

pi0 = vapour pressure in the pure state.

According to Raoult’s Law

p1 ∝ x1

And p1 = p1 0 x 1

Vapour Pressure of liquid solutions

A liquid solution is formed when a solvent is liquid. The solute can be gas, solid, or
liquid. Generally, In a solution, a liquid solvent is volatile. The solute may or may not.
Here we can discuss the properties of only binary solutions.

Vapour Pressure of Liquid Solutions and Raoult’s Law

(Raoult’s Law for volatile solutes)

Raoult’s Law states that the partial vapour pressure of each component in a solution of
volatile liquids is directly proportional to its mole fraction.

p1 ∝ x1

p1=p10x1

Where p10 is the vapour pressure of pure component 1 at the same temperature

Similarly for Component 2

p2=p20x2

Where p20 represents the vapour pressure of the pure component 2.

The total pressure p(total) over the solution phase in the container, according to
Dalton’s partial pressure law, is equal to the sum of the partial pressures of the
Solution’s components and is given as:

p(total) = p1 + p2
We get by substituting the values of

p(total )=x1p10 and x2p20

=p10+(p20−p10)x2

The minimum value of ptotal is p10, and the maximum value is p20, assuming p10 <
p20.

Let y1 = Mole fractions of component 1

y2 = Mole fractions of component 2

According to Dalton’s Law of partial pressures:

P1 = y1 ptotal

P2 = y2 ptotal

It is advised that while studying the class 12 Chemistry chapter 2 notes, students make
revision notes that will help them during the examination.

Vapour Pressures of Solutions of Solids in Liquids and Raoult’s Law

(Raoult’s Law for non-volatile solutes)

When a non-volatile solute is added to a solvent to make a solution, the number of

solvent molecules leaving the surface reduces the vapour pressure. Regardless of its
composition, the amount of non-volatile Solute present in the Solution determines the
drop in solvent vapour pressure. In its most general form, Raoult’s Law states that the
partial vapour pressure of each volatile component in a solution is directly proportional
to its mole fraction for every Solution.

p 1 ∝ x1

p1 = x1p10 = ptotal

The proportionality constant equals the vapour pressure of pure solvent, p10.

If Raoult’s Law obeys true for all concentrations, a solution’s vapour pressure will vary
linearly from zero to the pure solvent’s vapour pressure.

Ideal and Non-Ideal Solutions

Ideal Solutions: An ideal solution is one in which each component follows Raoult’s rule
over the entire range of temperature and concentration circumstances known as the
Ideal Solution.
 Properties of Ideal Solutions: Under class 12 Chemistry chapter 2 notes, the
properties of the ideal solution are given as

ΔmixH = 0

ΔmixV = 0

It means no heat is absorbed or evolved when the components are mixed.

 The enthalpy of mixing the pure components for the formation of the solution is 0.

So, Δmix H = 0.

 This means that heat is neither absorbed nor evolved during mixing components in a
solution.
 When pure components are mixed for the formation of the solution, then the volume is
also 0. Mathematically, Δmix V = 0
 The volume of the entire solution is = the sum of the volumes of the components.

Suppose the attractive intermolecular forces between the A-A and B-B molecules are
approximately comparable to those between the A-B molecules. An ideal solution is
rare, but some solutions are suitable for behaviour. For Example, n-hexane and n-
heptane solution, benzene and toluene solution fall into this category.

Non–Ideal solutions: When a solution deviates from Raoult’s Law over a broad
concentration range, it is known as a non-ideal solution. The solutions that don’t follow
Raoult’s Law at every concentration range and all temperatures are Non-Ideal
solutions.

Non-ideal solutions illustrate the below characteristics:

 The solute-solute and solvent-solvent interaction differ from that of the Solute-solvent
interaction
 The enthalpy of mixing i.e. is Δmix H ≠ 0, which means that heat might have been
evolved if the enthalpy of mixing is negative (Δmix H < 0), or the heat might have been
observed if the enthalpy of mixing is positive (Δmix H > 0)
 The mixing volume is Δmix V ≠ 0, which depicts that there will be some expansion or
contraction in the dissolution of liquids.

For more details of an ideal and non-ideal solution, students may refer to various other
study materials over and above Extramarks class 12 Chemistry chapter 2 notes.

Non-ideal solutions are categorised into two types:

i)Non-ideal solutions showing positive deviation from Raoult’s Law

ii) Non-ideal solutions showing negative deviation from Raoult’s Law

 i) Positive Deviation from Raoult’s Law: It occurs when the component’s vapour
pressure is more significant than what is expected in Raoult’s Law. For Example, we
consider two components, A and B, to create non-ideal solutions. So the vapour
pressure, pure vapour pressure, and mole fraction of component A is PA, PA0 and xA,
and that of component B be PB, PB0 and xB, respectively. These Liquids will present a
positive deviation when Raoult’s Law:

 PA > PA0 xA and PB > P0B xB, as the total vapour pressure (PA0 xA + P0B xB), is more
significant than what it should be according to Raoult’s Law.
 The solute-solvent forces of attraction are weaker than solute-solute and solvent-
solvent interaction, i.e., is, A – B < A – A or B – B
 The mixing enthalpy is +ve, which is Δmix H > 0. The heat absorbed to develop new
molecular interaction is less than the heat released to break the original interaction.
 The volume of mixing is +ve, that is, Δmix V > 0, as the volume expands on the
dissolution of components A and B.

Positive Deviation examples:

 Acetone and Carbon disulphide

 Acetone and Benzene
 Carbon Tetrachloride and Toluene or Chloroform
 Ethanol and Water
 Acetone and Ethanol
 Methyl alcohol and Water

ii) Negative Deviation from Raoult’s Law: It occurs when the total vapour pressure is
less than what it should be according to Raoult’s Law. We consider the same A and B
components to form a non-ideal solution. It will present a negative deviation only from
Raoult’s Law when:

 PA < PA0 xA and PB < P0B xB as the total vapour pressure (PA0 xA + P0B xB) is less
than what it should be concerning Raoult’s Law
 The solute-solvent interaction is more vital than the solute-solute and solvent-solvent
interaction, i.e. is, A – B > A – A or B – B
 The enthalpy of mixing is -ve, that is, Δmix H < 0 because more heat is released when
new molecular interactions are created.
 The volume of mixing is -ve, that is, Δmix V < 0 as the volume decreases on the
dissolution of components A and B.

Examples of solutions showing negative deviation from Raoult’s Law.

 Acetone and AnilineChloroform and Benzene

 Chloroform and Diether
 Nitric Acid ( HNO3) and water
 Acetic Acid and pyridine
 Hydrochloric Acid ( HCl) and Water

Students may refer to various other study materials in addition to class 12 Chemistry
chapter 2 notes to know more about Raoult’s Law.
 Azeotropes

Azeotropes are binary mixes that boil at the same temperature and have the same
composition in the liquid and vapour phases.

Minimum Boiling Azeotrope: Minimum boiling azeotrope at a specific composition is

formed by solutions that demonstrate a considerable positive departure from Raoult’s
Law.

For Example, an azeotrope with a boiling point of 351.15 K is formed by a mixture of

ethanol and water containing roughly 95% ethanol. The temperature at which water
boils – composition Large positive deviations are depicted in this diagram for solutions
(Minimum boiling azeotrope).

Maximum Boiling Azeotrope: Maximum boiling azeotrope at a specific composition is

formed by solutions that demonstrate a substantial negative divergence from Raoult’s
Law. A 68 per cent nitric acid and water mixture produces an azeotrope with a boiling
point of 393.5 K. The temperature at which water boils – composition Large negative
variances are depicted in this diagram for solutions. (Azeotrope with the highest boiling
point)

Colligative properties and determination of molar mass

Colligative is a Latin word that means ‘together binds’. Colligative properties depend
upon the number of solute particles in a solution, irrespective of their nature. More
details of colligative properties are shown in class 12 Chemistry chapter 2 notes NCERT
solution.

There are four colligative properties: a relative lowering of vapour pressure, elevation
of boiling point, depression of freezing point, and osmosis and osmotic pressures.

Related to these properties, the following deductions can be made:

1. Relative Lowering of Vapour Pressure

When a non-volatile solute is mixed with a solvent, the vapour pressure lowers. This
process is the lowering of vapour pressure. Raoult’s Law states that for a solution of
volatile liquid, the partial vapour pressure of each component in the solution is directly
proportional to its mole fraction. As per the laws created by scientists at that time,
lowering vapour pressure = vapour pressure of pure solvent – vapour pressure of the
solvent. We can determine the total molar mass of a solute through this equation.

(Psolvent = Xsolvent Posolvent)

Elevation of Boiling Point

The vapour pressure increases when a non-volatile solute is added with a solvent. The
boiling point of this solution is always more significant than the pure solvent to which it
is added. It is because the vapour pressure is indirectly proportional to the solution
temperature. If the solution needs to be boiled, the temperature of such a solution has to
be increased. This process comes to be identified as the elevation of the boiling point.
The solute particles and the vapour pressure simultaneously play a role in this
phenomenon.

Formula: ΔT = iKbm

Here ΔT= change in temperature

i = the van’t Hoff factor, which is the number of particles into which the solute dissolved

m = the molality, which is the moles of Solute per kilograms of solvent

Kb = the molal boiling point constant (for water, Kb = 0.5121oC/m)

Depression of Freezing Point

When the vapour pressure of a solution decreases, it reduces the freezing point of the
solution. The solution’s freezing point can be identified as a point where the vapour
pressure of a given substance is equal to liquid and the vapour state. As per Raoult’s
Law, the freezing point for a given dilute solution also stays directly proportional to the
molality of the solute, the same as the boiling elevation point.

Formula: ΔT = iKfm

Here ΔT= change in temperature

i = the van’t Hoff factor

m = the molality, which is the moles of Solute per kilograms of solvent

Kf = the molal freezing point constant (for water, Kf = -1.86 oC/m)

Osmosis and Osmotic Pressure

You may have observed raw mangoes shrivelling when placed in brine water or wilted
flowers reviving when placed in freshwater. Osmosis is the flow of solvent molecules
from pure solvent to the solution through a semipermeable membrane. The flow
continues until it reaches equilibrium.

The process of osmosis happens through a membrane that looks continuous but
contains tiny pores, which allow small solvent molecules like water to pass through, but
not bigger solute molecules. Such membranes are known as semipermeable membranes
(SPM). This pressure is known as the osmotic pressure of the Solution. Osmotic
pressure depends on the concentration of the Solution. The osmotic pressure is the
excess pressure applied to the Solution to prevent osmosis. It is also a colligative
property and depends on the number of solute molecules and not their identity.

Osmosis:-
When a semipermeable membrane separates a pure solvent and a solution, the solvent
particles move through the membrane from the solvent side to the solution side.
“Osmosis” is the name given to this phenomenon. The semipermeable membrane allows
only small molecules to pass through while blocking bigger solute molecules.

Osmotic Pressure: The excess pressure that must be given to a solution to prevent
osmosis, or the flow of solvent molecules through a semipermeable barrier into the
Solution, is known as the osmotic pressure of a solution. The osmotic pressure must be
equal to the excess pressure. To prevent osmosis, a coating should be put on the
solution.

Expression: At a given temperature T, osmotic pressure is proportional to the molarity,

C, of a dilute solution.

Thus:

π=C R T

Where π=osmotic pressure, C=molarity of the Solution, R=Universal Gas constant,

T=Temperature

Molarity can be calculated as the number of moles of solute per litre of the Solution.
Suppose w2 is the mass of Solute having molar mass M2 in a solution of volume V, then
we can write

π=w2RT/M2V.

We use the equation extensively to determine the molar mass of complex molecules of
proteins, polymers and other macromolecules. Scientists use this preferably for bio-
molecules as it shows a significant value even at room temperature.

Isotonic Solutions: Isotonic solutions are two liquids that have the same osmotic
pressure at the same temperature.

Compared to a more concentrated solution, a solution with a lower concentration or

lower osmotic pressure is “Hypotonic.”

Compared to a dilute solution, a solution with a higher concentration or higher osmotic

pressure is “hypertonic.”

Reverse Osmosis: The solvent will flow from the Solution into the pure solvent through
the semipermeable membrane if a pressure more significant than the osmotic pressure
is applied to the solution side. The process is known as reverse osmosis.

Application: Desalination of seawater: Pure water is squeezed out of the seawater

through the membrane when pressure greater than the osmotic pressure is applied.
Cellulose acetate is used as a permeable membrane to water but impermeable to
impurities, and ions are placed over support.
 Abnormal Molar Masses

The molecular mass is said to have aberrant molar mass when it is determined by
investigating any of the colligative qualities and differs from the theoretically expected
value. Some molecules of solvents with a low dielectric constant, like molecules of
ethanoic acid, dimerise into benzene due to a hydrogen bond. Association of all the
ethanoic acid molecules into benzene means Tb or Tf for ethanoic acid will be half the
standard value.

The molar mass calculated based on this ΔTb or ΔTf will be twice the expected molar
mass. This molar mass value is lower or higher than the expected or normal value and is
known as abnormal molar mass. In 1880 Jacobus Henricus van ‘t Hoff introduced
factor i, which was named the van’t Hoff factor. The van’t Hoff factor accounts for the
degree of dissociation or association.

The van’t Hoff factor ‘i’ can be explained as the ratio of Normal molar mass to the
abnormal molar mass.

Mathematically,

i= Normal molar mass / Abnormal molar mass

i = Observed colligative property / Calculated colligative property

i= Total number of moles of particles after association or dissociation/Number of moles

of particles before association or dissociation.

In addition, as explained in class 12 Chemistry chapter 2 notes,

 In the case of an association, the value of i is less than unity.

 In the case of dissociation, the value of i is greater than unity.
 Relative lowering of the vapour pressure of solvent =p10– p1 / p10 = i n2 / n1
 Elevation of Boiling point, ΔTb = i Kb m
 Depression of Freezing point, ΔTf = i Kf m
 The osmotic pressure of the Solution, ð = i n2RT/V

Dilution Law: When we dilute a solution with solvent, the amount of Solute remains
constant, and we can write:

M1 V1 = M2V2 & N1 V1= N2 V2

Molarity and Normality: Normality =Z x Molarity

Important Note: The temperature does not affect the mass percent, ppm, mole fraction,
or molality; however, temperature influences molarity and normality. This is because
temperature affects volume, whereas mass is not.

Solubility: The maximum or the highest amount of solute that can be dissolved in a
given amount of solvent given temperature is its solubility.
 The solubility of a solute in a liquid strongly depends upon the factors shown below.

 Nature of Solute
 Nature of the solvent
 The temperature of the Solution
 Pressure(Gases)
6. Introduction to Organic Chemistry
An organic compound is defined as any compound whose molecules contain carbon and
hydrogen ( also known as ” hydrocarbons” ) or compound that is the derivative of it. The
branch of science which deals with the scientific study of structure, properties and reactions of
hydrocarbons and their derivatives is known as organic chemistry.

Characteristics of Organic Compounds:-

The general characteristics of Organic Compounds include:

 Can be isolated as well as prepared in laboratory

 Comprise almost 90% of all known compounds.
 Mostly built up of only three elements- carbon, hydrogen and oxygen. Other
elements like halogen, nitrogen as well as phosphorous are also present but to a
lesser extent.
 Possess complex structures and high molecular weights
 Their properties are decided by certain active atom or group of atoms known as the
functional group.
 They are mostly insoluble in water but soluble in organic solvents.
 They are combustible in nature
 Chemical reactions involving organic compounds proceed at slower rates.

Characteristics due to Presence of Covalent Bonds:-

A covalent bond is a chemical bond that involves the sharing of electron pairs between atoms
that in turn results in a balance of attractive and repulsive forces between the atoms. The
presence of a covalent bond renders certain characteristics to the organic compounds. These
include:

 Low melting points and boiling points in comparison to the inorganic compounds.
 Organic acids and bases are less stronger and thus they have a limited dissociation
in an aqueous medium.
 They exhibit the phenomenon of isomerism in which a single molecular formula
represents several organic compounds differing in physical and chemical properties.
 They are volatile in nature.
General Characteristics of Members of Homologous Series

A Homologous Series is a group of organic chemical compounds, usually listed in the order of
increasing size, that have a similar structure (and hence, also similar properties) and whose
structures differ only by the number of CH2– CH2 units in the main carbon chain. They possess
the following general characteristics:

 A general formula describes the members of the homologous series

 Successive members differ from each other by CH2CH2
 Physical properties change regularly with increasing number of carbon atoms.
 Members have similar chemical properties because they have same functional
group.
 Members of the homologous series can be prepared using the same method.
Importance of Organic Compounds:-

 Organic compounds are important because all living organisms contain carbon.
 While carbohydrates, proteins and fats, the basic structures of life, are organic
compounds
 They are the basic components of many of the cycles that drive the earth. For
example, the carbon cycle that includes the exchange of carbon between plants and
animals in photosynthesis and cellular respiration.
 Organic compounds combine with metals to form organometallic compounds.
These compounds are important industrially. They are used as catalysts, promoters,
analysers as well as stabilizers.

Classification of Organic Compounds:-

Organic compounds constitute about 90% of all compounds. That’s quite a lot, isn’t it? In order
to study such a vast number of compounds, it is necessary to classify them into categories. Let
us know more about the Classification of Organic Compounds as well as the general categories
into which organic compounds are divided.

Depending upon the arrangement of carbon atoms in their structure, organic compounds are
broadly categorized into:-

1. Acyclic or Open Chain compounds

2. Cyclic or Closed Chain compounds

The following diagram will give you a clear idea about the classification of organic compounds:
 1. Acyclic or Open Chain Compounds

The carbon atoms are present in the form of an open chain.This chain may either be a straight
chain or a branched chain. These were initially known as Aliphatic compounds because the
compounds of this class were derived from either animal or vegetable fats

 Straight Chain Compounds: The carbon skeleton is in the form of a straight chain.
Examples:
n-Propane CH3-CH2-CH3

Propene CH2=CH-CH3

 Branched Chain Compounds: The carbon skeleton is in the form of a branched chain.

Examples: Isobutylene

2. Cyclic or Closed Chain Compounds

They are marked by the presence of one or more closed chains or ring of atoms in their
structure. Depending on whether there is a presence of any other atom apart from carbon in
the constitution of the ring, they are further classified as:

A. Homocyclic or Carbocyclic Compounds

B. Heterocyclic Compounds

A. Homocyclic or Carbocyclic Compounds:-

The rings in these compounds are entirely made up of carbon atoms. No other atom is present
in the ring skeleton.These can be further divided into two sub-classes:

 Alicyclic Compounds

 Aromatic Compounds

Alicyclic Compounds

Their name is attributed to their resemblance to Aliphatic compounds in their properties. The
examples of this category include cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc.
Aromatic Compounds

These are cyclic unsaturated compounds. They derive their name from the Greek
word Aroma which means “fragrant smell” since most of these compounds bear a pleasant
smell. These are further classified into two types:

 Benzenoid Aromatic Compounds: They are characterized by the presence of one or

more fused or isolated benzene rings as well as their derivatives in their structure.
Depending upon the number of benzene rings that are fused together in their structure,
they can be further classified as Monocyclic, Bicyclic, Tricyclic.

 Non-Benzenoid aromatic Compounds: They are characterized by the presence of a

single benzene ring to which other groups are attached.

Aniline

Bicyclic and Tricyclic Compounds

These are characterized by the presence of two or more rings in their structure.Examples
include Naphthalene, Phenanthrene as well as Anthracene.

Naphthalene

Phenanthrene

Anthracene

Non-Benzenoid Aromatic Compounds

Aromatic compounds that contain other highly unsaturated rings in place of the benzene ring
are called non-benzenoid aromatic compounds. Examples include

Azulene

Tropolone

B. Heterocyclic Compounds:-

When one or more heteroatoms such as oxygen, nitrogen, sulphur, boron, silicon etc, are
present in the ring such compounds are known as heterocyclic compounds.
 Alicyclic heterocyclic compounds: Aliphatic heterocyclic compounds that contain one
or more heteroatoms in their rings are called alicyclic heterocyclic compounds.

 Aromatic heterocyclic compounds Aromatic heterocyclic compounds that contain

one or more heteroatoms in their ring skeleton are called aromatic heterocyclic
compounds.

The Organic Functional Groups :-

Molecular Formulas

Alkanes are the simplest family of hydrocarbons - compounds containing carbon and
hydrogen only. Alkanes only contain carbon-hydrogen bonds and carbon-carbon single
bonds. The first six alkanes are as follows:
 methane CH4

ethane C2H6

propane C3H8

butane C4H10

pentane C5H12

hexane C6H14

You can work out the formula of any of the alkanes using the general formula CnH2n+2

Isomerism

Isomers are molecules that have the same molecular formula, but have a different
arrangement of the atoms in space. That excludes any different arrangements which are
simply due to the molecule rotating as a whole, or rotating about particular bonds. For
example, both of the following are the same molecule. They are not isomers. Both are
butane.

All of the alkanes containing four or more carbon atoms show structural isomerism,
meaning that there are two or more different structural formulae that you can draw for
each molecular formula.

There are also endless other possible ways that this molecule could twist itself. There is
completely free rotation around all the carbon-carbon single bonds. If you had a model
of a molecule in front of you, you would have to take it to pieces and rebuild it if you
wanted to make an isomer of that molecule. If you can make an apparently different
molecule just by rotating single bonds, it's not different - it's still the same molecule. In
structural isomerism, the atoms are arranged in a completely different order. This is
easier to see with specific examples. What follows looks at some of the ways that
structural isomers can arise.
Constitutional isomers arise because of the possibility of branching in carbon chains.
For example, there are two isomers of butane, C4H10. In one of them, the carbon atoms
lie in a "straight chain" whereas in the other the chain is branched.

Be careful not to draw "false" isomers which are just twisted versions of the original
molecule. For example, this structure is just the straight chain version of butane rotated
about the central carbon-carbon bond.

You could easily see this with a model. This is the example we've already used at the top
of this page.

Classification of Carbon and Hydrogen Atoms

Carbons have a special terminology to describe how many other carbons they are
attached to.

 Primary carbons (1o) attached to one other C atom

 Secondary carbons (2o) are attached to two other C’s
 Tertiary carbons (3o) are attached to theree other C’s
 Quaternary carbons (4o) are attached to four C's

For example, each of the three types of carbons are found in the 2,2 -dimethyl, 4-
methylpentane molecule
Hydrogen atoms are also classified in this manner. A hydrogen atom attached to a
primary carbon atom is called a primary hydrogen; thus, isobutane, has nine primary
hydrogens and one tertiary hydrogen.

 Primary hydrogens (1o) are attached to carbons bonded to one other C atom
 Secondary hydrogens (2o) are attached to carbons bonded to two other C’s
 Tertiary hydrogens (3o) are attached to carbons bonded to theree other C’s

Each of the three types of carbons are found in the 2,2 -dimethyl, 4-methylpentane
molecule

Nomenclature Of Organic Compounds:-

Nomenclature denotes the system of naming of organic substances. In case of aliphatic

compounds, two system of nomenclature frequently used are:

1) Trivial or common system

2) IUPAC system
 Trivial or common system

Organic compounds were named after the source from which they were initially isolated.

For example

Urea got its name as the compound was initially discovered from the urine of mammals

Methyl alcohol was termed wood spirit as it could be obtained by the destructive distillation
of wood.

Acetic Acid acquired its name from the acetum as it is present in vinegar.

Citric acid gets its name from the fact that it’s found in citrus fruits.

IUPAC system

To systematize the nomenclature of organic compounds, IUPAC system of nomenclature

was first established in 1947.

General Principles for IUPAC Nomenclature of organic compounds

The most major characteristic of this system is that any given molecular structure has just
one IUPAC name and any given IUPAC name implies only one molecular structure.

The IUPAC name of any organic compound primarily comprised of three parts

1. Word Root
2. Suffix
3. Prefix

Word Root– It specifies the number of carbon atoms contained in the parent chain (the
longest possible continuous chain of carbon atoms including the functional group and
numerous bonds) of the organic molecule.

Suffix – The two types of suffix are :

 Primary suffix : A primary suffix is always added to the word root to reflect whether the
carbon chain is saturated or unsaturated.
 Type of carbon chain Primary suffix

Saturated -ane

Unsaturated with one double bond -ene

Unsaturated with one triple bond -yne

If the parent chain has two, three, four or more double or triple bonds ,numerical prefixes
like as di, tri ,tetra are added to the prefect primary.

Type Of carbon chain Primary Suffix

Unsaturated with two double bonds -diene

Unsaturated with two triple bonds -diyne

 Secondary suffix : A secondary suffix is then added to the primary suffix to describe the
type of the functional group present in the organic compound.

Class of Organic compound Functional Group

Alcohols -OH

Aldehydes -CHO

Ketones -CO

carboxylic acid -COOH

Acid chloride -COCl

 While adding the secondary suffix to primary suffix ,the terminal e of the primary suffix is
omitted if the secondary suffix begins with a vowel but is kept if the secondary suffix begins
with a consonant.

Prefix

There are two types of prefixes:

1. Primary prefix : A primary prefix is used merely to distinguish cyclic from acyclic
compounds. For ex: In case of carbocyclic compounds, a primary prefix ,cyclo is used right
before the word root.
2. Secondary prefix : Certain groups are not regarded as functional groups but instead are
viewed as substituents. These are termed secondary prefixes and are added immediately
before the word roots in alphabetical sequence to denote the side chain or substituent
groups.

IUPAC name of an organic compound consist of: Secondary prefix+ Primary prefix+ Primary
suffix+ Secondary Suffix

structural isomerism:-
Structural isomerism is the phenomenon in which compounds have the same molecular
formula but different attachments of the ligands with the metal ions. Structural isomerism is
different from stereoisomerism in terms of spatial arrangements of atoms around the metal
and attachment of ligands with metal.

Structural isomerism can be classified into four different categories.

1. Ionisation Isomerism
2. Solvate Isomerism (Hydrate Isomerism)
3. Linkage Isomerism
4. Coordination Isomerism

Ionisation Isomerism

Coordination compounds having the same molecular formula but giving different types of
ions during dissociation in the aqueous solution is called ionisation isomerism. In this, the
ligand outside the coordination sphere replaces the ligands inside the coordination sphere,
generating a different compound. The difference between this isomerism can be identified
on the basis of the ions generated during the dissociation of the complexes in solution.

E.g.- [Co(NH3)5Br]SO4 is red-violet, [Co(NH3)5SO4]Br is red, [Co(NH3)5Br]SO4 will give a

white precipitate of BaSO4 when reacted with BaCl2 Solution, confirming the presence of
SO42- ion outside the coordination sphere.
 In this isomerism, the charge on the coordination complex is balanced, but both ligands are
necessary to balance the charge. The chemical properties of both the ligands are different
because ligands are different.

Solvate Isomerism

Coordination compounds having the same molecular formula, but different ligands in the
coordination sphere, due to the exchange of solvent molecules with the ligands in the
coordination sphere, is called Solvate isomerism. It is also called hydrate isomerism. It is a
special case of ionisation isomerization.

E.g:-
1. [Cr(H2O)6]Cl3 (violet)
2. [Cr(H2O)5Cl]Cl2.H2O (blue green)
3. [Cr(H2O)4Cl2]Cl.2H2O (green)

If we react Cr(H2O)6]Cl3, [Cr(H2O)5Cl]Cl2.H2O and [Cr(H2O)4Cl]Cl2.2H2O with the excess

amount of AgNO3, then the amount of AgCl is proportion to the number of Cl– ligands
outside the coordination sphere the quantitative analysis of AgCl mass will give an idea
about the number of Cl– ligands.

Linkage Isomerism
When coordination compounds have the same molecular formula but different kinds of
linkage due to the presence of ambidentate ligand, it is called linkage isomerism.
Ambidentate ligands can bind through two different sites but attach to the metal one site at
a time. (Ambidentate ligand is the necessary condition for this kind of isomerism, e.g., NO2–,
CN–, SCN–, S2O23-, and CO.

E.g- [CoONO(NH3)5]Cl2 (red) & [CoNO2(NH3)5]Cl2 (yellow), NO2– can bind with nitrogen as
well as oxygen. When bound through nitrogen NO2– (Nitro) and when bound through
oxygen –O-NO (nitrito).

Coordination Isomerism
In coordination isomerism, the exchange of ligands between cationic and anionic entities of
different metal ions, present in coordination compounds, occurs when a coordination
compound contains both cationic and anionic entities of the same metal ion. This type of
isomerism is only possible when cationic and anionic spheres differ in the distribution of
the ligands.
E.g- [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6] , [Pt(NH3)4][CuCl4] and
[Cu(NH3)4][PtCl4]

Ligand Isomerism
Some of the ligands can exist in two or more isomers (position isomerism ) for example,
diamino propane (exist as 1, 2-diamino propane (pn, CH3CH(NH2)CH2NH2) and 1, 3-diamino
propane (tn, H₂N(CH₂)₃NH₂), also known as trimethylene diamine.
Since ligands are coordinating from different sites in coordination complexes, it will
generate ligand isomers. E.g.- [Co(pn)2Cl2]+ and [Co(tn)2Cl2]+
Stereoisomerism

Stereoisomerism is a form of isomerism where compounds have the same molecular

formula and the same sequence of bonded atoms (connectivity) but differ in the three-
dimensional arrangement of their atoms in space. Stereoisomers can significantly impact
the physical and chemical properties of compounds, especially in biological systems.

1.0Types of Stereoisomerism

Stereoisomers are compounds with the same molecular formula and sequence of bonded
atoms but differ in the three-dimensional arrangement of their atoms. These differences
in spatial orientation lead to distinct physical and chemical properties. Stereoisomers can
be classified into two broad categories:

1. Configurational isomers

2. Conformational isomers.

2.0Configurational isomers

Configurational isomers are stereoisomers that can only be interconverted by breaking

and reforming chemical bonds. They are subdivided into Geometrical isomers and Optical
isomers.

1. Geometrical (Cis-Trans) Isomerism

2. Optical Isomerism

Geometrical (Cis-Trans) Isomerism:

Geometrical isomerism arises due to restricted rotation around a bond, typically a double
bond (C=C) or in cyclic compounds. In these isomers, the atoms or groups attached to the
carbon atoms of the double bond or ring are arranged differently in space.
  Cis Isomer: The same groups or atoms are on the same side of the double bond or
ring.

 Trans Isomer: The same groups or atoms are on the opposite sides of the double
bond or ring.

Conditions for Geometrical Isomerism:

 Restricted rotation around the double bond or ring structure.

 Different groups must be attached to the carbon atoms involved in the bond or ring.
If the two substituents are identical on both carbons, geometrical isomerism does
not exist.

 While a double bond often leads to geometrical isomerism (G.I.), it is not a necessary
condition. The key requirement for G.I. is restricted rotation around a bond or
structure, which can also occur in cyclic compounds where rotation is hindered.
Thus, restricted rotation is the critical condition for the existence of geometrical
isomers.

Example:

2-Butene:

 Cis-2-butene: CH₃ groups are on the same side of the double bond.

 Trans-2-butene: CH₃ groups are on opposite sides of the double bond.

Physical properties of Cis-Trans Geometrical Isomers:

S.No. Physical Property Cis vs. Trans Remarks

Cis-isomer has a
resultant dipole, while
1 Dipole Moment Cis > Trans
trans-isomer’s dipoles
cancel out.
Cis has stronger
intermolecular forces,
2 Boiling Point Cis > Trans
leading to a higher
boiling point.
Cis isomers are more
3 Solubility (in H₂O) Cis > Trans polar and dissolve
better in water.
Trans-isomers pack
better due to
4 Melting Point Trans > Cis
symmetry, leading to
higher melting points.
Trans isomers are
5 Stability Trans > Cis more stable due to
lower van der Waals
 strain.

Optical Isomerism

Optical isomerism occurs when molecules have the same connectivity but differ in how they
interact with plane-polarized light. Optical isomers, also known as enantiomers, are non-
superimposable mirror images of each other.

Chirality:

The key to optical isomerism is the presence of chirality. A molecule is said to be chiral if it
cannot be superimposed on its mirror image, much like left and right hands. A chiral center
(stereocenter) is usually a carbon atom bonded to four different groups.

 Enantiomers: These are two stereoisomers that are mirror images of each other but
cannot be superimposed. They have identical physical properties except for their
interaction with plane-polarized light and reactions in chiral environments.

Optical Activity:

Optical isomers (enantiomers) rotate the plane of polarized light in different directions:

 Dextrorotatory (d): Rotates light to the right (clockwise).

 Levorotatory (l): Rotates light to the left (counterclockwise).

R and S Nomenclature:

To distinguish enantiomers, the Cahn-Ingold-Prelog system is used to assign R or S

configuration to a chiral center. This system ranks the substituents around a chiral carbon
based on atomic number, and based on their arrangement, the isomer is classified as either
R (rectus) or S (sinister).

 R Configuration: The sequence of priorities follows a clockwise direction.

 S Configuration: The sequence of priorities follows a counterclockwise direction.

Diastereomers:

 Diastereomers are stereoisomers that are not mirror images of each other and are
non-superimposable. They differ in physical and chemical properties, unlike
enantiomers.

 They can occur when there are two or more chiral centers in a molecule.

Example of Enantiomers:

1. Lactic Acid: Lactic acid has one chiral center and exists as two enantiomers: D-
lactic acid and L-lactic acid.

2. Thalidomide: Thalidomide, a drug used in the 1950s, exists as two enantiomers.

One enantiomer had therapeutic effects, while the other caused severe birth defects,
illustrating the importance of chirality in pharmaceuticals.

Types of Optical Isomers:

Type of Optical Physical/Chemical

Description Example
Isomer Properties
Same physical
Non-superimposable
properties except D-lactic acid and L-
Enantiomers mirror images of each
direction of light lactic acid
other.
rotation.
Cis- and trans-
Stereoisomers that are Different physical and
Diastereomers isomers of tartaric
not mirror images. chemical properties.
acid

Meso Compounds: Meso compounds are stereoisomers that have multiple chiral centers
but are superimposable on their mirror image due to an internal plane of symmetry. As a
result, meso compounds are optically inactive.

Example:

 Tartaric Acid: It has two chiral centers and exists as two enantiomers (D and L
forms) and a meso form.
Key Differences Between Geometrical and Optical Isomerism

Property Geometrical Isomerism Optical Isomerism

Cis-trans isomerism based on Enantiomers or
Type of Isomerism spatial arrangement around a diastereomers, based on
double bond or ring. chiral centers.
Restricted rotation around a
Chirality (presence of a chiral
Cause bond (typically double bond
center).
or ring).
No effect on plane-polarized Rotates plane-polarized light
Plane-Polarized Light
light. (optically active).
Enantiomers, diastereomers,
Types Cis and Trans isomers.
and meso compounds.
Cis (same side), Trans R/S configuration (Cahn-
Nomenclature
(opposite side). Ingold-Prelog rules).

3.0Conformational Isomerism

Conformational isomers (or conformers) are stereoisomers that can be interconverted

by rotation around single bonds. Unlike configurational isomers, these do not require
breaking any bonds to convert from one form to another. Conformers typically occur in
alkanes and cycloalkanes due to the free rotation about C–C single bonds.

Key Types of Conformational Isomers:

1. Staggered Conformation:In this conformation, the atoms or groups attached to the

two carbons are positioned as far apart as possible, leading to minimized repulsion
and maximum stability. Ethane and cyclohexane are common examples that show
staggered conformations.

2. Eclipsed Conformation:In this conformation, the atoms or groups are aligned with
one another, leading to maximum repulsion and higher energy. This is less stable
than the staggered conformation.

Example- Conformation of Propane

4.0Strain related to Conformational Isomers

Strain refers to the instability in a molecule caused by the repulsion or unfavorable

interactions between atoms or groups. The strain affects the molecule’s stability and
reactivity. There are several types of strain in organic chemistry, each arising from different
structural aspects of molecules.

Type of Strain Cause Example Effect

Eclipsed bonds
Eclipsed conformation Increased energy,
Torsional Strain leading to electron
of ethane decreased stability
repulsion
Repulsion between
Bulky groups being Gauche conformation
Steric Strain large groups,
too close of butane
instability
Bond angles deviating Increased energy,
Angle Strain Cyclopropane
from ideal values bond angle distortion
Combination of
Cyclobutane, Decreases stability of
Ring Strain torsional, angle, and
cyclopropane cyclic compounds
steric strain in rings

Aromatic Compounds
Aromatic compounds are any member of a vast family of chemical compounds that are
unsaturated and have the characteristic of having one or more planar rings of atoms that are
connected by covalent bonds of two distinct types. The aromaticity of these compounds refers
to the one-of-a-kind stability that they possess.

Aromatic Compounds:-

Aromatic compounds are a kind of chemical molecule that lack distinct alternating single and
double bonds and instead comprise conjugated planar ring systems with delocalized pi-electron
clouds. Arenes and aromatics are two more names for these compounds. Benzene is the most well-
known representative of aromatic chemicals. These are unsaturated molecules that are not easily
broken down in their natural environments.

Significance of Aromatic Compounds

Aromatic compounds have consistently played a crucial part in elevating the standard of living
throughout human history, and this trend is not likely to change anytime soon. Components used in
computers and DVD players, as well as pivotal elements of automobile parts, are all constructed of
aromatic compounds. Aromatic compounds include commonly used medications like aspirin and
paracetamol. These substances have been around for a very long time.

Aromatic Compounds Examples

Benzene and toluene are well-known aromatics. Benzene has a single aromatic ring. Toluene is
benzene with a methyl group. Coal and petroleum provide the most simple aromatic chemicals.
Volcanic activity, forest fires, and fuel-burning create aromatic chemicals. They’re also in crude oil.
Aromatic chemicals have a pleasant fragrance. Toluene and benzene smell nice, while aniline stinks
like rotting fish. 4,4′-Methylenedianiline is an odourless aromatic chemical (MDA).

Huckel’s Rule of Aromaticity

Huckel’s Rule uses the number of electrons (N) and the ring structure to identify whether
a molecule is aromatic, anti-aromatic, or non-aromatic.

The following procedure determines the number of electrons in the aromatic system.

N=4n+2 for some n(integer).

The following procedure determines the number of electrons in the anti-aromatic system.

N=4n for integer n(integer).

Non-aromatic compounds lack a planar conjugated p-orbital ring.

Huckel’s Rule evaluates a ringed molecule’s aromatic potential. Planar ring requirements may need
further research.

Properties of Aromatic Compounds

 Aromatic Hydrocarbons come from oil and coal. Physical and chemical characteristics
are exceptional.
 High carbon-hydrogen ratio. High carbon concentration causes a sooty yellow flame.
 Electrophilic and nucleophilic aromatic substitutions occur.
 Aromatic hydrocarbons are stable because of resonance and electrophilic substitution.
In these reactions, the carbon ring functions as a nucleophile and an electrophile to
attack benzene.

Classification of Aromatic Compounds

1. Nuclear Substituted Compounds

Nuclear-substituted compounds are aromatic compounds with a substituent or functional group
directly connected to the benzene ring.

2. Side-chain-substituted compounds
Side chain substituted aromatic compounds have functional groups in the ring’s side chain. Phenyl
derivatives of aliphatic chemicals.
IUPAC Nomenclature of Aromatic Compounds

Single substituents on benzene rings with six or fewer carbons are prefixed to benzene. Alkyl
groups are designated according to the alkane series convention ending with -yl: methyl (1
carbon), ethyl (2 carbons), propyl (3 carbons), etc. If the substituent has more than six carbons, we
mention the alkane component first. 1-phenyloctane is bound to an 8-carbon chain, not octyl
benzene. Ring atoms are numbered to limit the number of substitution places. Ortho- is used if the
substituents are near (1,2), meta- if they are separated by one ring position (1,3), and para- if they
are on opposing sides of the ring (1,4).

Arene and Aryl Groups

The term “arenes” refers to a functional group that includes benzene, benzenes that have been
substituted, and polybenzenes. It is common to practice to refer to substituted benzenes by such
nomenclature. One may refer to the relative positions as 1,2- = ortho-, 1,3- = meta-, and 1,4- = para-
substitution. An aryl group, denoted by the symbol “Ar,” is the fragment that results from the
removal of a hydrogen atom that is directly attached to a benzene ring in an arene.

An aryl group has a point of attachment on a carbon atom that is not occupied. In organic
chemistry, an arene is any monocyclic or polycyclic aromatic hydrocarbon, while an aryl is any
univalent organic radical produced from an aromatic hydrocarbon by removing a hydrogen atom.
Arenes and aryls both fall within the category of aromatic hydrocarbons.

Aromaticity

Any planar system with full delocalisation of the pi-electron in the ring and 4n+2 pi electrons in the
ring is said to be aromatic. Aromaticity is a feature that may be found in any system that has this
property. Example: Benzene, naphthalene, anthracene, etc. Conjugated cycloalkenes that have the
attribute of aromaticity have a molecule that is more stable as a result of the capacity of electrons in
the orbitals to delocalize. Aromaticity is a property of conjugated cycloalkenes. To construct a
planar molecule, this serves as a kind of framework.

Benzene

Benzene(C_6H_6), is the most basic organic and aromatic hydrocarbon and serves as the parent
component of a large number of significant aromatic compounds. The manufacturing of
polystyrene is the primary use for benzene, which is a liquid that lacks colour and has an easily
recognizable odour. It is known to induce cancer and has a high level of toxicity; being exposed to it
may result in leukaemia.

Benzene is a liquid aromatic hydrocarbon that is odourless, colourless, transparent, very

combustible, and volatile. Benzene may be found in crude oils, as a by-product of the procedures
used to refine oil, as a solvent, and as an ingredient in the production of a wide variety of chemicals.
It comes into being as a result of both natural processes and the actions of humans.

Aniline
Aniline looks like a yellowish to brownish liquid that is oily and smells like fishy mould. Melts at -
6°C, boils at 184°C and catches fire at 158°F. It has a density of 8.5 lb/gal and is only slightly soluble
in water. Heavier than air vapours. Toxic if breathed in or absorbed through the skin.

Aspirin

Aspirin is made by acetylating salicylic acid with acetic anhydride, which is a chemical process.
It has a mol weight of 180.16g/mol. It has no smell and can be clear crystals or white powder.
Hybridization is the concept of mixing atomic orbitals that are close in energy to form same number of new hybrid
orbitals with equal energy and definite geometry. These newly formed orbitals are called hybrid orbitals.

The concept of hybridization was first proposed by Linus Pauling in 1931.

Important points of hybridization-

 The hybridization of atomic orbitals takes place either by

reshuffling of all or some of the orbitals in the excited state. +
s px
 The hybrid orbitals have same shape, size and energy i.e. they
are equivalent to each other.

 The number of hybrid orbitals is equal to the number of

reshuffled pure atomic orbitals. + +
 The shape, size, orientation and energy content of the hybrid
s px py
orbitals are different from the pure atomic orbitals.

 The labels given to hybrid orbitals reflect the contributing

atomic orbitals. For example- an sp hybrid orbital possess equal
amounts of s and p orbital character.
+ + +
s px py pz
Bonding in methane

In methane, carbon is in sp3 hybridised state where it has four sp3 hybridised orbitals

Each four sp3 hybrid orbitals of carbon overlap with half-filled 1s orbitals of four H atoms to form four C-H bonds. All the four C-
H bonds in methane are equivalent with 1.10 Å. All of the H-C-H bond angles are 109.5º
Bonding in ethane
In ethane, both the carbon atoms are sp3 hybridised. In its structure, three of the sp3 hybrid orbitals of each carbon atom overlap
with the 1s orbitals of H to form a total of six C-H bonds, while the remaining sp3 hybrid orbital of carbon overlap with the sp3
hybrid orbital of adjacent carbon to form C-C sigma bond.

Bonding in ethylene
In ethylene, each carbon atom is in sp2 hybridised state.
In its structure, each carbon atom utilized two of its three sp2 hybrid orbitals to form two C-H bonds by overlaping with the 1s
orbitals of H. The remaining sp2 hybrid orbitals of each carbon overlap with each other along the axis to form C-C sigma bond.
The unhybridised 2pz orbital, perpendicular to the plane of sp2 hybrid orbitals overlap sidewise with the other 2pz orbital on the
adjacent carbon.

Bonding in acetylene
In acetylene, carbon atoms are sp hybridised.
In the formation of acetylene, one sp hybrid orbital on each carbon overlaps with 1s orbital of hydrogen to form C-H sigma bond,
while the other sp hybrid orbital of carbon atom overlaps with the sp hybrid orbital of adjacent carbon atom along the axis to form
C-C sigma bond. The remaining two unhybridised 2p orbitals (2py and 2pz) of each carbon overlap with each other side wise to
form two pi bonds.

Table 1: Shape of the molecules depending on hybridisation

Hybridisation Molecular geometry Example

sp3 Tetrahedral CH4

sp2 Planar trigonal C2H4, BCl3

sp Linear C2H2, BeH2

Influence of hybridization on bond properties

Table 2: Comparison of bond angles, bond length and bond strengths of C-C and C-H bonds in ethane, ethene and ethyne

Molecule Hybridisation Bond angles C-C bond Strength of C-H bond Strength of
of carbon length (Å) C-C bond length (Å) C-H bond
(Kcalmol-1) (Kcalmol-1)
Ethane sp3 109.5º 1.54 88 1.10 101

Ethene sp2 120º 1.33 152 1.08 107

Ethyne sp 180º 1.20 200 1.06 131

 When comparing lengths and strengths of C-C single, double and triple bonds, the more bonds holding two carbon atoms
together, the shorter and stronger the C-C bond.

 The more s character in hybridisation, the shorter and stronger the bond, because an s orbital is closer to the
nucleus than a p orbital.

 C-H bond is shorter and stronger than C-C sigma bond. The s orbital of H is closer to the nucleus than is the sp3 orbital of
carbon, so the carbon and H nuclei are closer together in sp3-s overlap than are the carbon nuclei in sp3-sp3 overlap, causing
C-H bond to be shorter than a C-C bond.

 Bond angle in a molecule depends primarily on the shape of the molecule. The more s character in an orbital used by
carbon or any atom to form the bond has, the larger the bond angle of the molecule.

 The hybridization of C, O or N atom can be determined by the number of pi bonds it

forms. If it forms no pi bonds, it is sp3 hybridised; if it forms one pi bond, it is sp2
Important points
hybridised and; if it forms two pi bonds, it is sp hybridised.
of hybridization-
 The hybridisation of C, O or N is sp(3-number of pi bonds).
 Bonding in methyl cation (CH3+)

A positively charged carbon forms three covalent bonds, so it hybridizes three orbitals- one s and two p
orbitals. Therefore, it forms three covalent bonds by using the three sp2 orbitals. The unhybridized p orbital
remains empty. So, the structure of carbocation is trigonal planar. The p orbital stands perpendicular to the
plane.

Bonding in methyl radical (CH3.)

The carbon atom in methyl radical is also sp2 hybridised. The unpaired electron is in the p orbital.

Bonding in methyl anion (CH3-)

The negatively charged carbon has three bonding and one nonbonding electron pairs. Since, pairs of
electrons should be placed as far apart from each other as possible, the four orbitals containing the electron
pairs point towards the corners of a tetrahedron. In other words, the negatively charged is sp3 hybridised.
Three of the sp3 hybrid orbitals overlap with the s orbital of H and the fouth sp3 orbital holds the non-bonding
electron pair.
 Bonding in water (H2O)

In water, oxygen atom is sp3 hybridised. Each of the two O-H bonds is formed by the overlap of an sp3 orbital of oxygen with 1s
orbital of hydrogen. The remaining two sp3 hybridised orbitals are occupied by the two nonbonding pair of electrons.

The bond angle in water is a little smaller (104.5º) than the tetrahedral angle, because of the lone pair-bond pair and lone pair-
lone pair repulsion which reduces the bond angle.
7.Organic Reaction Mechanism:-
Organic chemistry is the chemistry of carbon compounds except for oxides of carbon and
metal carbonates. Carbon has the uncommon characteristic of forming strong bonds with
many other elements, particularly with other carbon atoms, to form chains and rings, giving
rise to millions of organic molecules. Carbon compounds are essential for the survival of life
on Earth because of this distinguishing property. Proteins, DNA (deoxyribonucleic acid),
and other complex organic substances provide chemical, structural, or genetic functions in
living beings.
A chemical equation only shows the starting and final products of a reaction; it rarely shows
how the process proceeds. Some reactions occur through intermediates, which may or may
not be separated depending on their stability.
Mechanism is the complete step-by-step description of the order in which bonds break and
bonds form, to give the observed products.

Electron Movement in Organic reactions

Curved arrows are used to depict electron transport in chemical processes. The curving
arrow is a handy indication for showing bonding changes caused by electronic
redistribution during the reaction. A covalent connection is created when two atoms share a
pair of electrons. The many methods in which the electron-pair travels are depicted below
using curved arrows. The arrow begins at the point when the electron-pair is displaced and
ends at the point where the electron-pair travels.
 Shifting of electron-pair from π-bond to adjacent bond position.

 Shifting of electron-pair from π-bond to adjacent atom.

 Shifting of electron-pair from atom to adjacent bond position.

For Example: In the case of ethane when reacting in presence of UV light, due to the
electron shifting, two methane molecules are obtained as shown below,
Bond Fission
In any chemical reaction, when a reactant is converted into products one or more bonds in the
reactant are broken and new bonds are formed. The process of breaking or cleavage of a
covalent bond is known as bond fission.

Now, the bond fission takes place in two ways as mentioned below,
Homolytic fission
The symmetrical breaking of a covalent bond between two atoms such that each atom
acquires one electron of the shared pair is called homolytic fission or homolysis.

Such fission takes place in the presence of ultraviolet light or at high temperatures. The
cleavage of a bond results in the formation of free radicals. A free radical is a neutral species
(atom or group) that contains an unpaired electron. Homolytic fission can be shown as,

The movement of a single electron is shown by a half-headed curved arrow (Fishhook). Free
radicals have transitory existence i.e. they are short-lived and are highly reactive. They
are paramagnetic.
Generally, a covalent bond between two atoms of the same element or two atoms having
nearly the same electronegativity breaks in this manner. For example, Organic reactions
which proceed by homolysis are called free radical or homopolar or non-polar reactions as
these reactions take place in a non-polar solvent. Homolysis generally occurs in the gaseous
phase in presence of sunlight or ultra-violet light or in the presence of catalysts such as
hydrogen peroxide.
Heterolytic fission
The unsymmetrical breaking of a covalent bond between two atoms such that the more
electronegative atom acquires both the electrons of the shared pair is called heterolytic fission
or heterolysis.

Such fission takes place in the presence of a polar solvent. The cleavage of a bond results in
the formation of ions. One of the ions has a sextet electronic structure and a positive charge
called a cation and the other ion has a valence octet with at least one lone pair and a
negative charge called an anion.
Heterolytic fission can be shown as,
 where B is more electronegative than A.
If A is more electronegative than B, then the fission will be shown as,

The ions formed are unstable and reactive. An example of heterolysis is,

The species in which a carbon atom possesses a sextet of electrons and a positive charge is
called carbocation or carbonium ion. A carbocation is electron deficient. In the C-Br bond,
the bromine atom is more electronegative than the carbon atom and hence the electron pair
is retained by the bromine atom on fission.
But consider the reaction:

In the C-H bond, the carbon atom is more electronegative than the hydrogen atom and
hence the electron pair is retained by the carbon atom on fission. The species in which a
carbon atom possesses an octet of electrons and a negative charge is called carbanion.
Carbanions are reactive as they are unstable. Organic reactions which proceed by
heterolytic are called ionic or heteropolar or simply polar reactions as these reactions take
place in a polar solvent. Heterolysis is uncommon in a gaseous state.
What are Free Radicals?
An uncharged species which is electrically neutral and contains a single electron is called free
radical.
Free radical is highly reactive and therefore has a transitory existence i.e. it is short-lived.
Consider methyl radical in which carbon is sp3 hybridized and has a planar structure. H – C –
H bond angle is 120 degrees The odd electron is in the p orbital which P is perpendicular to the
plane of three C – H bonds (refer to the image shown below).
Carbon is electron deficient as it has only seven electrons in the valence shell.
The structure of the methyl radical is like that of the methyl cation, except there is an
additional electron.

What are Reagents?

The reagent reacts with the substrate to give products. The reagent may be an electron-rich or
electron-deficient chemical species that attacks the substrate during a chemical reaction.
The following are two types of important reagents.
1. Electrophilic reagents or electrophiles: Electrophiles are electron-deficient species.
They are either positively charged species like H, NO₂, etc. or molecules containing the
central atoms having incomplete octet of electrons in their outermost orbit like BF, AICI,
ZnCl₂, etc. Since electrophiles are electron-deficient, they accept a pair of electrons from
donor atoms and thus they are electron loving reagents. All electrophiles are basically
Lewis acids.
2. Nucleophilic reagents or nucleophiles: Nucleophiles are electron-rich species. They are
either negatively charged species like OH, CN, CT, Br etc. or molecules containing at least
one lone pair of electrons on the central atom-like H₂O, NH₂, H₂S, R OH, R-NH₂, R-OR, etc.
Since nucleophiles are electron-rich, they donate a pair of electrons to acceptor atoms and
thus they are nucleus loving reagents. All nucleophiles are Lewis bases.

Electromeric Effect: Electronic Displacements in a Covalent Bond

The displacement of electrons in a molecule’s covalent bond occurs either as a result of the
presence of a suitable attacking reagent or as a result of the impact of an atom or a
substituent group in the ground state.
Temporary electron displacements are observed when a reagent approaches the molecule,
and this form of electron displacement is known as the electromeric effect. Electron
displacements caused by an atom or a substituent group in the molecule create permanent
polarisation of the bond. This form of electron displacement is exemplified by the inductive
effect.
Electronic displacements in a covalent bond can cause bond fission under certain
conditions. For instance, homolytic and heterolytic fission.
Inductive effect
Lets first understand the two important types of covalent bonds as,
 Non-polar Bonds: When a covalent bond is established between two atoms of the same
element or two atoms with the same electronegativity, the bonding pair of electrons is
shared equally by the two atoms. This type of bond is non-polar in nature. Examples of
such bonds are, H – H, Cl – Cl, O = O, etc.
 Polar bonds: When a covalent bond is established between atoms of different elements
with different electronegativity values, the electron density in the bond shifts towards
the more electronegative atom. A polar covalent bond is formed when the electron
density shifts. Examples are, H – CI, H – OH, H3C – Cl, etc.
Consider chloroethane, which has the formula CH3 – CH2 – Cl. It is polarised such that
carbon number one receives a positive charge (+δ) and chlorine gains a negative charge (-
δ). An arrow pointing from +δ to -δ of the polar bond depicts the shift in electron density.

C1, which has generated a positive charge (+δ), attracts electron density from the nearby C –
C bond. As a result, some positive charge (+δ1) occurs on C2, where +δ1 represents a
significantly lower positive charge than that on C1. In other words, the polar C – Cl bond
causes the neighbouring bonds to become polar. Such polarization of sigma (σ) bond caused
by the polarization of adjacent sigma bond is referred to as the inductive effect.
It is a long-term consequence. This impact is carried on to succeeding bonds as well,
although it diminishes fast as the length of the carbon chain rises. After bonding, the effect is
very negligible.
As a result, the electron pairs, although being permanently relocated, remain in identical
valence shells.

The capacity of substituents to remove or give electron density to the connected carbon
atom is related to the inductive effect. Based on this capacity, substituents can be classed
as:
 -I Effect (Negative Inductive Effect) – Atoms or groups of atoms that are highly
electronegative or carry positive charge are electron-withdrawing groups and such
groups are said to have (-I) effect. For example, -F, -Cl, -Br, -I, -NO2, -CN, -COOH, -COOR, -
SO3H, etc are the electron-withdrawing groups. The higher the electronegativity of an
atom, the greater is the -I effect e.g. the -I effect decreases in the order F > Cl > Br > I.
Positively charged atoms or groups have greater, -I effect than neutral atoms or groups
e.g. -N+O2 has more -I effect than -NH2
 +I Effect (Positive Inductive Effect) – Atoms or groups of atoms that are
electropositive or carry negative charge are electron-donating groups and such groups
are said to have (+I ) effect. Metals like Na, K, Mg, Zn, etc., and alkyl groups such as -CH3,
– CH2CH3, -CH(CH3)2, etc. are electron-donating groups. The negatively charged groups
such as CH3O-, C2H5O-, etc. show a strong +I effect. Less electronegative elements have a
greater +I effect e.g. Be > B > C. Similarly, negatively charged atoms or groups have a
greater +I effect than neutral atoms e.g. CH3 – CH2 > CH3 – CH3.
Electromagnetic Effect
 Certain chemicals produce polarity in non-polar covalent bonds or improve polarity in
polar covalent bonds. This is known as the electromeric effect.

The electromagnetic effect is a temporary effect, but it aids in increasing the reactivity of the
molecule by inducing or boosting the polarity of the substrate with numerous bonds.
Resonance
When a carboxylic acid loses a proton, the electron density is shared by both oxygen atoms –
the electrons are delocalized. Delocalized electrons are not bound to a single atom or a link
between two atoms. A compound having delocalized electrons is said to have resonance.

The two structures that use localized electrons are known as resonance
contributors, resonance structures, resonance forms, or contributing resonance
structures. Neither of these resonance forms is the right structure for a carboxylate ion.
The real structure, which is a hybrid of the two structures, is known as a resonance hybrid,
and it is depicted with dotted lines to demonstrate that electrons are delocalized.
Resonance forms are represented by a double-headed arrow.

Resonance Form

Resonance Hybrid
The negative charge (electrons) is distributed across both oxygen atoms. Each oxygen atom
bears half of the negative charge, which stabilizes the ion. The carbon-oxygen bonds have a
bond order of 11/2, which means they are halfway between a single bond and a double
bond. Electron delocalization happens only when all of the atoms that share the delocalized
electrons are in or near the same plane, allowing their p orbitals to overlap efficiently.
Note: The only difference between the two resonance forms of carboxylate ion is the
placement of their π electrons and lone-pairs; all of the atoms remain in the same spot.

In short, resonance, also called mesomerism, refers to the phenomena in which compounds
exist in a state that is a mixture of two or more electronic structures, each of which appears
equally capable of expressing most of the attributes of the compound but none of which
describes all of the qualities.
Resonance Stabilization: The resonance hybrid structure has lower energy than any of the
contributing resonance structures. The energy difference between the real structure
(resonance hybrid) and the lowest energy resonance structure is referred to as resonance
stabilization energy, or simply resonance energy. The resonance energy increases as the
number of key contributing resonance structures increases.
Resonance in Benzene

Structure of Benzene

 In the below two images, each benzene resonance form clearly demonstrates that the ring
has six π electrons. The resonance shapes are only a handy technique to portray the π
electrons; they do not represent any actual electron distribution. In benzene, for example,
the link between C-1 and C-2 is neither a double bond as indicated in figure1 nor a single
bond as shown in figure 2.

 It falls somewhere in the middle of the two resonance forms. The resonance hybrid, which
is the average of the two resonance forms, is the true structure of benzene.
Resonance in Nitroethane

Resonance Form

 In the above image, the double bond in the 1st structure is the single bond and in the 2nd
structure, it’s vice versa.

Resonance Hybrid

 The resonance hybrid shows that the two nitrogen-oxygen bonds are identical and the
negative charge is shared by both oxygens. The p orbital of nitrogen overlaps the p orbital
of each oxygen. In other words, the two electrons are shared by three atoms.

Rules for drawing resonance structure

1. Only the electrons move; the nuclei of the atoms never move, therefore the bond angles
must stay constant.
2. The only electrons that can travel are π electrons and lone pairs.
3. The number of unpaired electrons, if any, must stay constant. Most stable compounds
have no unpaired electrons, and all electrons must stay coupled in all resonance
structures.
4. The resonance contributor with the least energy is the most important. Good
contributions often have all octets completed, as many bonds as feasible, and as minimal
charge separation as possible. Negative charges are more stable on more
electronegative elements such as O, N, and S.
5. Resonance stabilization is particularly essential when it serves to delocalize a charge
across two or more atoms.
Electrons can be moved in one of the following ways –
 Move π electrons towards a positive charge or towards a π bond:

(movement of π electron toward a positive charge)

(movement of π electron toward a π bond)

 Move a lone pair of electrons towards an π bond:
 Move single non-bonding electron towards π bond:

On the basis of electron transfer the Resonance Effect is classified in two as:
 Positive resonance (+R) effect: The positive resonance effect occurs when electrons
are transferred away from an atom or substituent group connected to the conjugated
system. For example, the +R effect in aniline
Because of the electron transmission across the chain, specific sites in the molecule have
high electron concentrations, which explains the reactivity at these places. The groups that
reflect the +R electron displacement effect include halogen, -OH, -OR, -NH2, -NHR, -NR2, -
NHCOR, OCOR, and so on.
 Negative resonance (-R) effect: The negative resonance effect occurs when electrons
are transferred towards the atom or substituent group connected to the conjugated
system. For example, -R effect in nitrobenzene

Some of the groups that exhibit the -R electron displacement effect are -COOH, -CHO, -CN,
and so on.
Hyperconjugation
Hyperconjugation is the delocalization of electrons caused by the overlap of a p-orbital and a
sigma (σ) bond (α C-H).

Only when the σ bond and the vacant p-orbital are properly oriented does hyperconjugation
occur. Sigma bond electrons form a partial conjugation with an unshared p-orbital or the
connected unsaturated system. It is a long-term impact with a stabilizing effect.
 Consider the ethyl cation CH3CH2. The positively charged carbon atom possesses six
electrons, is hybridized sp2, and has an unfilled p orbital. One of the nearby methyl
 group’s C – H bonds is aligned with the plane of the vacant p-orbital. The electrons of the
σ bond (this C-H bond) delocalize into the vacant p orbital, stabilizing the cation.

 Because of the overlap, the positive charge is diffused by the electron density of the
surrounding σ bond, which stabilizes the cation. Hyperconjugation can be depicted as,

 The more alkyl groups connected to a positively charged carbon atom, the stronger the
hyperconjugation connection and the more stable the cation. As a result, the relative
stability of the following cations diminishes with increasing order.
(CH3)3 C+ > (CH3)2 CH > CH3 CH2 > CH3
 This is due to the fact that tert-butyl cation has nine hyperconjugation structures,
isopropyl cation has six, and ethyl cation has three. Because the vacant p orbital in
C+H3 is perpendicular to the plane in which the C-H bonds are located, the overlap is not
conceivable. As a result, C+H3 lacks hyper-conjugative stability.
 Electron delocalization through hyperconjugation is also feasible in alkenes and
aromatic compounds such as alkyl arenes. Hyperconjugation in propene, for example, is
seen in the below figure.