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RAJIV GANDHI COLLEGE OF ENGINEERING AND TECHNOLOGY, PUDUCHERRY B. Tech.

First Year – Semester I (2023-2024)
CHEMISTRY -PART B
UNIT I
1. Schrodinger equation application to Particle in a box
Schrodinger equation
Time-independent Schrödinger equation.
^
HΨ=EΨ
 Where H is called Hamiltonian operator,
 Ψ is the wave function and, is a function of
position co-ordinates of the particle and is
denoted as Ψ (X,Y,Z)
 E is the energy of the system
 The above schrodinger wave equation does not
contain time as a variable and is referred to as
time independent Schrödinger wave equation

2. Particle in a box
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3.Applications for Conjugated Molecules and Nanoparticles

Schrodinger equation applications to conjugated (-C=C-C=C-) systems:
 Conjugated molecules, such as polyenes, have alternating single and double bonds which result in
delocalized π-electrons.
 The particle in a box model can approximate the behavior of these π-electrons. For example, the energy
levels and transitions between them can be used to predict the absorption spectra of these molecules.
 Energy Absorption: The difference in energy levels (ΔE) corresponds to the energy of absorbed photons,
and thus the wavelength of light absorbed. This helps in understanding UV-visible spectra of conjugated
systems.
 Molecular Orbitals: The spatial variable x will be displacement along the -C=C-C=C- molecular backbone,
the box length L can be approximated by the length of the conjugated system, influencing the energy level
spacing and providing insight into the electronic properties of the molecule.
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Schrodinger equation applications to Nanoparticles

 For nanoparticles, the particle in a box model is used to describe quantum confinement effects.
 When the size of the particle is comparable to the de Broglie wavelength of electrons, the energy levels
become quantized.
 Quantum Dots: These are semiconductor nanoparticles where the quantum confinement leads to discrete
energy levels. The color of light emitted or absorbed can be tuned by changing the size of the quantum dot,
which affects L and thus the energy levels.
 Electronic Properties: The size-dependent electronic properties are crucial for applications in
optoelectronics, such as LEDs and solar cells. By controlling the size, one can tailor the electronic and
optical properties of the nanoparticles for specific applications.
 In summary, the solutions of the Schrödinger equation for a particle in a box provide a useful model for
understanding and predicting the behavior of conjugated molecules and nanoparticles, particularly their
electronic and optical properties.

4. Explain the Forms of the hydrogen atom and the plots to explore their spatial variations
Forms of the hydrogen atom wave functions and the plots to explore their spatial variations
The wave functions of the hydrogen atom are solutions to the Schrödinger equation in spherical coordinates.
They are characterized by three quantum numbers: n (principal quantum number), l (azimuthal quantum
number), and ml (magnetic quantum number). The general form of the hydrogen atom wave function is:
ψn,l,ml(r,θ,ϕ)=Rn,l(r)⋅Yl,ml(θ,ϕ)
Where: Rn,l(r) is the radial part, dependent on r (the radial distance),
Yl,ml(θ,ϕ) are the spherical harmonics, dependent on θ (the polar angle) and ϕ (the azimuthal angle).
Radial Part: Rn,l(r) The radial wave functions Rn,l(r) are solutions to the radial part of the Schrödinger
equation and involve the associated Laguerre polynomials. They determine the probability distribution of
finding an electron at a distance r from the nucleus.
Angular Part: Yl,ml(θ,ϕ)
The spherical harmonics Yl,ml(θ,ϕ) describe the angular part of the wave function and depend on the quantum
numbers l and ml
Plots to Explore Spatial Variations
Schrödinger proposed the quantum mechanical model of the atom, which treats electrons as matter waves.
Schrödinger's equation,
H ^ ψ = E ψ,
Can be solved to yield a series of wave function, each of which is associated with an electron binding energy
These types include 1s, 2s, 3p, and Angular Wave Functions. The Hydrogen Wave Function's derivation
involves solving Schrodinger's time-independent equation, leading to a wave function representing the different
energy states of the hydrogen atom.
The hydrogen atom wave functions ψ(r,θ,ϕ) can be expressed as a product of radial and angular functions. The
angular part is simply the spherical harmonics depend on the quantum numbers l and ml.

Radial Probability Density

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The radial probability density is the function plotted to show the likelihood of finding an electron at a distance r
from the nucleus.
Angular Probability Density
The angular probability density is given by the square of the spherical harmonics:
This density describes how the probability varies with the angles θ and ϕ.
Combined Plots
By combining the radial and angular parts, the full spatial distribution of the electron probability density can be
visualized. These plots show the regions in space where an electron is likely to be found.

Probability Densities: Often visualized as 3D plots or contour plots, these illustrate the electron cloud's shape
and orientation.
Radial Plots: help in understanding the distribution of the electron at different distances from the nucleus
Angular Plots: 2D and 3D plots show the angular dependence of the electron's position.
These visualizations are crucial for understanding the spatial variations and the shapes of atomic orbitals, which
have significant implications for chemical bonding and the properties of atoms and molecules.
For a 1s or for that matter, any orbital electron, the probability of finding the electron at the nucleus is zero.
Therefore, the ratio of probabilities of finding the electron at the nucleus to the first Bohr's orbit a0 is zero since
probability is zero at the nucleus.
The spatial wave function of two indistinguishable particles is a mathematical function that describes the
probability of finding the two particles at different positions in space

5. Draw MOT diagram for CO & NO and show the bond

order and magnetic character.
MO energy level diagram for a CO molecule.
Electronic configuration of C atom: 1s2 2s2 2p2 Electronic
configuration of O atom: 1s2 2s2 2p4 Electronic configuration
of CO molecule : σ1s2, σ1s*2, σ2s2, σ2s*2, π2p 2, π2p 2 σ2p 2
y z x
Bond order = 1/2(Nb−Na)
Nb = No. of electrons in bonding orbitals
Na = No. of electrons in anti-bonding orbitals
Bond order = Nb−Na/2 =10−4/2 =3 The molecule has no
unpaired electrons hence it is diamagnetic.

MO energy level diagram for a NO molecule.

Electronic configuration of N atom: 1s2 2s2 2p3 Electronic
configuration of O atom: 1s2 2s2 2p4 The electronic configuration
of NO =
σ(1s2)σ∗(1s2)σ(2s2)σ∗(2s2)σ(2pz)2π(2px)2π(2py)2π∗
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(2px)1π∗ (2py)
Bond order = 1/2(Nb−Na)
Nb = No. of electrons in bonding orbitals
Na = No. of electrons in anti-bonding orbitals Bond order =10−5/2 Bond order = 2.5 Hence, the bond order of
NO will be 2.5
The molecule has one unpaired electrons hence it is paramagnetic.

4. Arrange the following molecules in order of their increasing bond order O2, O2+, O2-.
Bond order:
 The bond order can be calculated as half
the difference between the number of
electrons in nonbonding (bonding-free)
and bonding-filled molecular orbitals.
The formula for calculating bond order:
Bond order = 1/2(Nb−Na)
Nb = No. of electrons in bonding orbitals
 Na = No. of electrons in anti-bonding
orbitals

6. Pi molecular orbitals of butadiene

Pi-Molecular Orbitals of 1,3-Butadiene
 1,3-Butadiene contains two double bonds that are conjugated.
 It is "built" from 4 sp2 hybridsed C atoms, each contributing a p atomic orbital containing 1 electron.
 An alternative way to consider "building" the π molecular orbitals is by combining the π molecular
orbitals of two ethene molecules. This requires that we make an in-phase and an out-of-phase
combination for both the π and π* of ethene.
 Either way, we end up with the same set of 4 π molecular orbitals.
 Notice how the number of nodes and the number of anti-bonding interactions increases as you go up the
diagram above
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7. Pi molecular orbitals of aromaticity ( benzene)

Pi-Molecular Orbitals of Benzene:

 Benzene has a planar hexagonal structure in which all the six carbon atoms are sp2 hybridized.
 Four valency electrons of each carbon atom, three forms covalent bonds with two carbon atoms and one
hydrogen atoms.
 The remaining cyclic six p-orbitals (one on each carbon) overlap to generate six molecular orbitals,
three bonding and three antibonding. molecular orbitals of benzene
 The wave equation of benzene is
 ᴪ = ᴪ 1C1+ ᴪ2 C2+ ᴪ 3C3+ ᴪ4C4+ ᴪ5 C 5 + ᴪ6 C6
 Where ᴪ 1 to ᴪ 6 are the wave functions of six Pz –orbitals.
 C1 to C6 are their respective coefficients.

8. Aromaticity
Aromaticity is defined as a property of the conjugated cycloalkenes which enhances the stability of a molecule
due to the delocalization of electrons present in the π-π orbitals.
Conditions for Aromatcity or Hückel's Rule
If a cyclic, planar molecule has 4n+2 π electrons, it is considered aromatic..
Example: Benzene, naphthalene, anthracene,

8. Using CFT, draw energy level diagram, write electronic configuration of the central metal atom/ion
and determine the magnetic moment value in the
following (a) [CoF6]3− ,[Co(CN)6]3−
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[CoF6]3− F− is a weak field ligand.

Configuration of Co3+=3d6(or t2g4 eg2)
Number of unpaired electrons (n)=4
Magnetic moment (μ)=√n(n+2)=√4(4+2)=√24=4.9BM

,[Co(CN)6]3−
,[Co(CN)6]3− i.e., Co3+
∵ CN is strong field ligand.
Co3+=3d6(or t2g6 eg0)
There is no unpaired electron, so it is diamagnetic.
μ=0
9. Using CFT, draw energy level diagram, write electronic configuration of the central metal atom/ion
and determine the magnetic moment value in the
following [FeF6]3−, [Fe(CN)6]4−
[FeF6]3−,
[FeF6]3−, F− is a weak field ligand Number of
unpaired electrons, n=5
μ=√5(5+2) =√35=5.92BM

[Fe(CN)6]4−
[Fe(CN)6]4− Since, CN− is a strong field ligand, all the
electrons get paired.
Fe2+=3d6(or t2g6 eg0)
Because there is no unpaired electron, so it is
diamagnetic in nature.

10. On the basis of CFT, write the electronic configuration of d4 in terms of t2g and eg in an octahedral
field when (i) Δ0>P (ii) Δ0<P
If Δ0<P, the correct electronic configuration for d4 system will be -
the electronic configuration for d4 system will be t2g3 eg1

If Δ0>P, the correct electronic configuration for d4 system will be -

the electronic configuration for d4 system will be t2g4 eg0

11. Discuss the band theory of solids with digram

Band Theory Of Solids
A useful way to visualize the difference between conductors, insulators and semiconductors is to plot the
available energies for electrons in the materials. Instead of having discrete energies as in the case of free atoms,
the available energy states form bands.
Energy Bands in Solids
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In the band theory of solids, there are many energy bands but the following are the three most important energy
bands in solids
 :Valence Band
 Conduction Band
 Forbidden Band
Valence band
The energy band that consists of
valence electrons energy levels, is
known as
the valence band. The valence band
is present below the conduction band
and the electrons of this band are
loosely bound to the nucleus of the atom.
Conduction band: The energy band that consists of free electrons energy levels, is known as the conduction
band. For electrons to be free, external energy must be applied such that the valence electrons get pushed to the
conduction band and become free.
Forbidden band
The energy gap between the valence band and the conduction band is known as the forbidden band which is
also known as the forbidden gap. The electrical conductivity of a solid is determined by the forbidden gap and
also the classification of the materials as conductors, semiconductors, and insulators

Conductors are those substances through which electricity can flow are called conductors. Some common
conductors are copper, aluminum, gold, and silver.
Insulators are those substances through which electricity cannot flow are called insulators. Some common
insulators are glass, plastic, rubber, and wood.
Semiconductors are materials which have a conductivity between conductors (generally metals) and
nonconductors or insulators (such as most ceramics). Semiconductors can be pure elements, such as silicon or
germanium, or compounds such as gallium arsenideBand model of doped semiconductors
Fermi energy gap
The gap between the valence band and conduction band is called Fermi energy gap
In conductor, the valence band and conduction band overlap,so there is no band gap.
In insulators there is large band gap between valence band and conduction band.
In semiconductor, there is a small band gap between valence band and conduction band.so the electrons can
promote from V.B to C.B with rise in temperature or by adding dopants

12. What is Doping? What are the different types of doping

. Dopant:
A dopant also called a doping agent is a trace impurity element that is inserted into a substance(in very low
concentrations) to increase the electrical properties of the substances.
. Doping
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 In semiconductors there is a small enough gap between the valence and conduction bands that thermal or
other excitations can bridge the gap. With such a small gap, the presence of a small percentage of a doping
material can increase conductivity dramatically.
 The process by which impurity is adding in semiconductor to enhance their conductivity is called doping
 Two of the most important materials silicon can be doped with, are boron (3 valence electrons = 3-valent)
and phosphorus (5 valence electrons = 5-valent).
 Other materials are aluminium, indium (3-valent) and arsenic, 

antimony (5-valent)..

 Elements with 3 valence electrons are used for p- type doping,

5-valued elements for n-doping. 
n-doping 
 The 5-valent dopant has an outer electron more than the silicon
atoms. Four outer electrons combine with ever one silicon
atom, while the fifth electron is free to move and serves as
charge carrier.
 This free electron requires much less energy to be
lifted from the valence band into the
 conduction band, than the electrons which cause the
intrinsic conductivity of silicon.
 The dopants are positively charged by the loss of
negative charge carriers Doped semimetals whose
conductivity is based on free (negative) electrons are n-
type or n- doped.
Due to the higher number of free electrons those are also
named as majority chargecarriers,
 .
p-doping:
 In contrast to the free electron due to doping with phosphorus, the 3-valent dopant effect is exactly the
opposite. The 3-valent dopants can catch an additional outer electron, thus leaving a hole in the valence
band of silicon atoms.
 Therefore the electrons in the valence band become mobile. The holes move in the opposite direction
to the movement of the electrons. .
 With the inclusion of an electron, the dopant is negatively charged, such dopants are called acceptors.
 Due to positive holes these semiconductors are
 called p-conductive or p-dopents
UNIT II
1. Give the selection rules for various spectroscopy and What is mean by Jablonski diagram?
SELECTION RULES
Refers to the condition that tells us about the transitions that are possible (or allowed)
Selection rules of Rotational (Microwave) spectroscopy
(i) A molecule must have a permanent dipole moment
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(ii) Transition in rotational energy is limited to adjacent levels

ΔJ = ± 1 where J is rotational quantum number
.
Selection rules of Vibrational (IR) spectroscopy
(i) Vibrations are only IR active (or allowed), if molecular dipole moment changes during vibration.
(ii) For Harmonic oscillator ∆v = ±1
For anharmonic oscillator ∆v = ±1, ±2, ±3 …where ν is vibrational quantum number

Rotational-vibrational spectra
Infra-red light absorbed only when a change in dipole character of molecule takes place. If a molecule has a
centre of symmetry, then vibrations are centro symmetric and inactive in the infra-red but are active in the
Raman. The vibrations which are not centro symmetric are active in infra-red but inactive in Raman.

. Selection rules of electronic (UV-visible) spectroscopy

(i) Only π to π* and n to π* transitions occur in the UV-Vis region are observed.
(ii) σ to σ* transition requires an absorption of a photon with a wavelength which does not fall in the UV-Vis
range.

Selection rules of NMR spectroscopy

The selection rule for NMR spectra is Δm = ±1 where m is
magnetic quantum number
This means that only transitions in which m changes by one (up or
down) are allowed. For a nucleus with I=1/2, there is only one
allowed transition. For nuclei with I >1/2, there are multiple
transitions which can take place.

2. What is mean by Jablonski diagram

Jablonski diagram of Fluorescence
Absorption of a photon by fluorophore raises an electron to an excited
energy state. Within this state, the electron drops to ground level via
radiationless vibrational relaxation.
3. Explain principle and Medical applications of Fluorescence spectroscopy
Principle of fluorescence spectroscopy
Interaction of photons with molecules results in promotion of valence electrons from ground state orbitals to
high energy levels, said to be in excited state.
Molecules in excited state do not remain there long but spontaneously relax to more stable ground state.

The relaxation process is brought about by collisional energy transfer to solvent or other molecules in the
solution. Some excited molecules however return to the ground state by emitting the excess energy as light.
This process is called fluorescence.
Advantages
Up to 1% can be achieved easily in Flourimetric.
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The method is very sensitive and also possesses specificity because there is a choice of wavelength not only for
the radiation emitted, but also for the light which excites it.
Limitations
Careful buffering is necessary as fluorescence intensity may be strongly dependent
Ultraviolet light used for excitation may cause destruction of the fluorescent molecule.
The presence of dissolved oxygen may cause increased photochemical destruction.
Traces of iodide and nitrogen oxides are efficient quenchers and therefore interfere.
All elements and compounds are unable to exhibit fluorescence.

Medicinal Application of Fluorescence

 It is an emerging tool for medical diseases including pre-malignant and malignant lesions.
 It is a non-invasive technique and has been applied successfully for the diagnosis of
 multisystem cancers with high sensitivity and specificity.
 It is used to perform kinetics measurements, detect intracellular ion concentrations, analyze the rotational
motion of molecules using polarizing filters, and for temperature-controlled protein and peptide analysis.
 Used as a non-destructive way of tracking or analysis of biological molecules (proteins)
 Possible direct or indirect analysis of aromatic amino acids (alanine-tyrosine-tryptophan)
 Fingerprints can be visualized with fluorescent compounds such as ninhydrin
 Accurate determination of glucose: Abnormal amount of glucose provides significant
 information of many diseases such as diabetes or hypoglycemia.

4. Discuss about Rotational Spectroscopy (Microwave Spectroscopy)

MICROWAVE SPECTROSCOPY (Rotational spectroscopy)
In microwave spectrometer, a microwave source, usually a klystron valve, produces a beam that is passed
through a gaseous sample. The beam then impinges on the detector, usually a crystal detector, and signal
(wavelength against intensity) is displayed, as printed plot or on oscilloscope.

PRINCIPLE
A microwave spectrum is obtained by sweeping the microwave source over a range of frequencies and
observing the small variations in power at the detector. An absorption line appears as a sharp dip on the
recording system. To increase the sensitivity of a microwave spectrometer, Stark modulation may be added.
It is based on the principle that microwave radiation causes changes in the rotational energy levels of molecules
and absorption consequently occurs at characteristic frequencies.
. Selection rules of Rotational (Microwave) spectroscopy
(i) A molecule must have a permanent dipole moment
(ii) Transition in rotational energy is limited to adjacent levels
ΔJ = ± 1 where J is rotational quantum number

Degrees of Freedom
Polyatomic molecules may exhibit more than one fundamental vibrational absorption bands.
Total degrees of freedom = 3n
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Translational degrees of freedom =3

Rotational degrees of freedom =2
Vibrational degrees of freedom = 3n-3-2 = 3n - 5

In the case of non-linear molecule, there are three degrees of rotation

Total degrees of freedom = 3n
Translational degrees of freedom = 3
Rotational degrees of freedom =3
Vibrational degrees of freedom = 3n-3-3 = 3n-6

APPLICATIONS
Microwave spectroscopy is suitable for studying chemically and physically very interesting molecular systems,
including weakly bound complexes, radicals, ions, and other transient species. Information on molecular
structure, internal motions and intermolecular interactions are easily obtained.
Limitations
The chief disadvantage of microwave spectroscopy for gas-phase analytical applications is that its sensitivity is
not as high as for some other methods (such as laser fluorescence or mass spectrometry).

5. Discuss about vibrational spectroscopy (IR Spectroscopy)

Vibrational and rotational spectroscopy: INFRARED SPECTROSCOPY (IR)
Change in the vibrational motion of molecule is absorbed in the Infrared region, also called as Infrared
Spectroscopy. If vibration in the molecule persists then it should change its dipole moment that may be the
magnitude form or oriented with its direction.
Principle
 Absorption of energy by a molecule in infrared region brings about changes in vibrational and rotational
energy levels of the molecule.
 IR spectroscopy is otherwise known as vibrational spectroscopy. A single vibrational energy change is
accompanied by a large number of rotational energy changes. Thus, vibrational spectra appear as
vibrational-rotational bands.
 Ordinary infrared region extends from 4000 - 667 cm-1.
 The region from 12500 - 4000 cm-1 is called near infrared.
 The region from 667 - 50 cm-1 is called far infrared.
Finger Print Region
The region to right-hand side of diagram (from about 1500 to 500 cm- 1) usually contains a very complicated
series of absorptions. These are mainly due to all manner of bending vibrations within the molecule. This is
called the finger print region.

. Number of Fundamental Vibrations of diatomic molecules

Polyatomic molecules may exhibit more than one fundamental vibrational absorption bands. Number of these
fundamental bands is related to degrees of freedom in a molecule..
3n degrees of freedom = Translational + Rotational + Vibrational
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In the case of linear molecule there are only two degrees of rotation. Eg. CO2
Vibrational degrees of freedom = 3n-3-2 = 3n - 5

In case of non-linear molecule, there are three degrees of rotation as the rotation about all three axes will result
in a change in position of the atoms.
Vibrational degrees of freedom = 3n-3-3 = 3n-6

Selection Rules
Infra-red light absorbed only when a change in dipole character of molecule takes place. If a molecule has a
centre of symmetry, then vibrations are centro symmetric and inactive in the infra-red but are active in the
Raman. The vibrations which are not centro symmetric are active in infra-red but inactive in Raman.

Applications of IR spectroscopy
1. To determine hydrogen bonding, molecular symmetry, dipole moments, bond length, etc.
2. Used in measuring degree of polymerization in manufacturing polymers.
3. Used in Forensic labs and used in Organic and Inorganic chemistry
4. Identification of functional group and structure elucidation

6. Write the principle and Medical Applications of MRI Spectroscopy

MAGNETIC RESONANCE IMAGING (MRI)
This is the medical imaging technique which is used in radiology to form pictures of anatomy and physiological
process of body. This technique uses very strong magnetic fields and high radio waves to generate organs
image.
MRI is a medical application of NMR that can also be used for imaging in other NMR applications such as
NMR spectroscopy.
MRI uses a powerful magnetic field, radio waves and a computer to produce detailed pictures of the body's
internal structures that are clearer, more detailed. In some instances to identify and accurately characterize
disease than other imaging methods.

MRI Components
(i) Main magnet: A superconducting coil that polarizes the sample
(ii) Gradient coils: Localize the region to be scanned
(iii) Radiofrequency (RF) coils: Excite the sample and detect the resulting NMR
(iv) Computer system: Controls and coordinates the component

Applications of MRI
MRIs are used in a variety of clinical applications, including:
(i) Imaging injuries: MRIs are often used to image shoulder and knee injuries
(ii) Diagnosing brain conditions: MRIs can diagnose tumors and aneurysms, and differentiate between grey
matter and white matter in the brain
(iii) Monitoring treatment effects: MRIs can monitor the effects of treatments on diseases of various organs
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(iv) Biopsy and thermal therapy: MRIs can be used to perform biopsies and thermal therapy on the brain and
other parts of the body
Advantage
(i) MRI are non-destructive and non-invasive and do not emit ionizing radiation (x-rays &CT scans)
(ii) MRI uses radiation in the radiofrequency range which is found all around us and does not damage tissue as
it passes.

7. Explain in detail any two surface characterization techniques

The surface of a solid in contact with a liquid or gaseous phase usually differs substantially from the interior of
the solid both in chemical composition and physical properties. Characterization of these surface properties is
of vital importance in a number of fields, heterogeneous catalysis, sensor development and application, and
semiconductor thin-film technology.
It also aids in understanding, corrosion and adhesion mechanisms, activity of metal surfaces, embrittlement
properties, and behavior and functions of biological
membranes.
Principle
The solid surface is irradiated with a primary beam. Beam
may be photons, electrons, ions, or neutral molecules.
Impact of primary beams on a surface results in formation of a
secondary beam (photons, ions, e- or molecules) that are scatterred, sputterred or emitted from solid surface.
Surface characterization techniques
Electron spectroscopy
In electron spectroscopy, the spectroscopic measurement consists of the determination of the power of the
electron beam as a function of the energy (or frequency hv) of the electrons. The most common type is based
upon the irradiation of the sample surface with monochromatic X- Ray radiation. This is called X-ray
photoelectron spectroscopy (XPS). This method is also known as Electron spectroscopy for chemical analysis
(ESCA).
The second type of electron spectroscopy is called Auger electron spectroscopy (AES). Auger spectra are most
commonly excited by a beam of electrons,
although X-rays are also used.
The third type of electron spectroscopy is
ultraviolet photoelectron spectroscopy (UPS). In
this method, a monochromatic beam of ultraviolet
radiation causes the ejection of electrons form the
analyte. This method is not as common as the first
two methods.
Applications
 Used for the identification of all of the
elements in the periodic table except for
helium and hydrogen.
 The determination of the oxidation state of an element and the type of species to which it is bonded.
 15

 Provides useful information about the electronic structure of molecules.

.
Secondary-ion mass spectrometry (SIMS)
 Secondary-ion mass spectrometry (SIMS) is the most
highly developed of the mass spectrometric surface
methods, with several manufacturers offering
instruments for this technique.
 SIMS is useful for determining both atomic and
molecular composition of solid surfaces.
 In secondary-ion mass analyzers that serve for general
surface analysis and for depth profiling, the primary
ion beam diameter is from 0.3 to 0.5mm.
 Double-focusing, single-focusing, time-of-flight and
quadrapole spectrometers are used for mass
determination.

UNIT III
1. Derive the Nernst Equation and How cell potential is measured?
Nernst equation
An expression relating electrode potential of an electrode to concentration of its ions in solution has been given
by Nernst equation.
Derivation
Consider a redox reaction: Mn+ + n e – M
For a reversible reaction, free energy change (G) and its equilibrium constant (K) are inter related as, G =
RT ln K + RT ln [Product] / [Reactant] where R is gas constant and T is temperature.
When concentrations of reactants and products are unity, then,
G = RT ln K where G is standard free energy change.
Therefore G = G + RT ln [Product] / [Reactant]
This equation is popularly known as Vant Hoff reaction isotherm.
In a reversible reaction, electrical energy is produced at the expense of free energy decrease. Let E be the
electrode potential forms between metal and solution of its own salt of valency n.
Now the electrical energy required for transferring 1 g equivalent of metal ion from metal to solution of its own
salt would be nFE.
Thus, decrease in free energy of a metal will produce nFE electrical energy.
i.e. – G = nFE
where G is free energy change; F is Faraday; n is valence electrons; E is electrode potential.
At standard condition – G = nFE where E is the standard electrode potential
Substituting the values of G and G in the Vant hoff equation,
– nFE = – nFE + RT ln [M] / [Mn+]
as concentration of metal, M is unity
– nFE = – nFE + RT ln 1 / [Mn+]
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– nFE = – nFE – RT ln [Mn+]

dividing the above equation by – nF, we get,
E = E + (RT / nF) ln [Mn+]
Converting ln to log,
E = E + (2.303 RT / nF) log [Mn+]
This expression is known as Nernst equation for electrode potential.
At 25C, R = 8.314 J/K/mole; F = 96,500 Coulombs; T = 25C, Nernst equation becomes,
E = E + (0.0591 / n) log [Mn+] at 25C
Inference
(i) If concentration of solution is increased, electrode potential increases.
(ii) If temperature increases, the electrode potential increases.

2. How cell potential is measured

Cell potential refers to the voltage of an electrochemical cell whose
value can be affected by temperature, concentration, and pressure..
Calculation of cell Potential
The standard potential for any cell can be calculated by subtracting the
standard reduction potential of the half-reaction occurring at the anode
from the standard reduction potential of the half-reaction occurring at
the cathode.
Using E of anode half-cell and cathode half-cell, the cell potential
(standard e.m.f.) can be calculated.
EX
A galvanic cell is formed of Cu and Ag in which the reaction occurs as follows –
Cu(s) + 2Ag+ Cu2+ + 2Ag,
2+ +
E°Cu /Cu = 0.34V, EºAg /Ag = 0.80V.
Ecell = Ecathode – Eanode
Ecell = 0.80– 0.34
Ecell = 0.46 V

3. Write note on Cell potential and its applications

Cell Potential or EMF series and its applications
Electrochemical series is the arrangement of various electrodes in increasing order of their standard electrode
potential.

Examples Half-cell E (V) Nature

2+
Zn /Zn – 0.76 Anodic
H+/H2 0.00 Reference
Cu2+/Cu + 0.34 Cathodic

Applications of Cell Potential and EMF series.

 17

(i) Relative ease of oxidation or reduction

Relative tendencies of the metals to get ionized into solution can be noted from electrochemical series. A
system with higher value of standard reduction potential has a greater tendency to undergo reduction. The
positive sign indicates reduction reaction.
(ii) Replacement tendency
Higher value of reduction potential shows a greater tendency to assume the reduced form. For example, to
know whether Cu will displace Zn from solution or vice-versa, the answer is derived from electrochemical
series.
(iii) Predicting spontaneity of redox reaction
From the e.m.f. (E) value of complete cell reaction, spontaneity of the redox reaction can be predicted. Thus,
(a) if G = – ve E = + ve cell reaction is feasible, i.e., spontaneous
(b) if G = + ve E = – ve cell reaction is non-spontaneous
(c) if G = 0 E=0 cell reaction is in equilibrium.

(iv) Calculation of standard e.m.f. of the cell

Using E of anode half-cell and cathode half-cell, the standard e.m.f. can be calculated.
Ecell = Ecathode – Eanode

(v) Calculation of equilibrium constant

Standard electrode potential, G = RT ln Keq
By substituting the value of G
nFE = RT ln Keq
log Keq = (nE / 0.0592 V)
(vi) Displacement of Hydrogen
Metal with negative reduction potential will displace hydrogen from an acid solution.
Zn + H2SO4 ZnSO4 + H2 (E of zinc = – 0.76 V)
Metal with positive reduction potential will not displace hydrogen from acid solution.
Ag + H2SO4 no reaction (E of silver = + 0.8 V)
(vii) Nature of Corrosion
The anodic metals or more active metals in the electrochemical series are more prone to corrosion. The
cathodic metals or more noble metals are less prone to corrosion.
4. Write note on Henderson – Hasselbalch equation (Acid-base Equilibrium)
Henderson – Hasselbalch equation (Acid-base Equilibrium)
The concentration of hydronium ion in an acidic buffer solution depends on the ratio of the
concentration of the weak acid to the concentration of its conjugate base present in the solution i.e.,
 18

5. Explain Briefly The common ion effect

The common ion effect
A salt of a weak acid is added to the acid itself, the dissociation of the weak acid is suppressed further.
For example, the addition of sodium acetate to acetic acid solution leads to the suppression in the dissociation
of acetic acid which is already weakly dissociated. In this case, CH 3 COOH and CH3 COONa have the common
ion,CH3 COO-
Let us analyse why this happens. Acetic acid is a weak acid. It is not completely dissociated in aqueous solution
and hence the following equilibrium exists.

However, the added salt, sodium acetate, completely dissociates to produce Na+ and CH COO- ion.

Hence, the overall concentration of CH3 COO-

We know from Le chatelier's principle that when a stress is applied to a system at equilibrium, the system
adjusts itself to nullify the effect produced by that stress. So, inorder to maintain the equilibrium, the excess
CH3 COO- ions combines with H+ ions to produce much more unionized CH 3 COOH i.e, the equilibrium will
shift towards the left.
. Thus, the dissociation of a weak acid (CH3COOH) is suppressed in the presence of a salt (CH 3COONa)
containing an ion common to the weak electrolyte. It is called the common ion effect.

6. Van Der Waals Equation Derivation For Real Gases

Compressibility factor
The compressibility factor is a correction coefficient that describes the deviation of a real gas from ideal gas
behaviour. It is usually represented with the symbol z
The compressibility factor for an ideal gas z=1 always. For a non-ideal gas at any
given pressure, z can be higher or lower than one,
VAN DER WAALS EQUATION DERIVATION FOR REAL GASES
Gases that obey the equation PV=nRT under all conditions are called ideal
gases.
But in practice there is no ideal gas. Gases tend to behave ideally at high temperatures and at low
pressures.
For real gases, van der Waals modified the ideal gas equation as
follows
Pressure Correction:
The pressure of a gas is directly proportional to the force
created by the bombardment of molecules on the walls of the
 19

container. Hence, the measured gas pressure is lower than the ideal pressure of the gas. Hence, van der
Waals introduced a correction term to this effect.
Van der Waals found out the forces of attraction experienced by a molecule near the wall are directly
proportional to the square of the density of the gas. where n is the number of moles of gas and V is the
volume of the container where a is proportionality constant and depends on the nature of gas,
Therefore,

Volume Correction
As every individual molecule of a gas occupies a certain volume, the actual volume is less than the volume of
the container, V. Van der Waals introduced a correction factor V' to this effect. Let us calculate the correction
term by considering gas molecules as spheres.

The constants a and b are van der Waals constants and their
values vary with the nature of the gas. It is an approximate
formula for the non-ideal gas.

Therefore, replacing the corrected pressure and volume in the

ideal gas equation PV=nRT we get the van der Waals equation
of state for real gases as below,

Significance or merits of van der Waals equation

 The equation of Van der Waals can tell the behavior of gas easily in a better and more accurate way than
ideal gas equation.
 Also used and are accurate to fluids, not just to gases.

7 Explain Solubility Equlibria with example and its applications

Solubility Equlibria
The equilibrium constant for an equilibrium involving the precipitation or dissolution of a slightly soluble ionic
solid is called the solubility product, Ksp, of the solid.
For a heterogeneous equilibrium involving the slightly soluble solid M𝑝X𝑞 and its ions Mm+ and Xn−:
M𝑝X𝑞(𝑠)⇌𝑝Mm+(𝑎𝑞)+𝑞Xn−(𝑎𝑞)
the solubility product expression is:
𝐾sp=[Mm+]𝑝[Xn−]𝑞
The solubility product of a slightly soluble electrolyte can be calculated from its solubility; conversely, its
solubility can be calculated from its Ksp,
 20

The Solubility Product

The solubility of a substance can vary from essentially zero (insoluble or sparingly soluble) to infinity
(miscible). A solute with finite solubility can yield a saturated solution when it is added to a solvent in an
amount exceeding its solubility, resulting in a
heterogeneous mixture of the saturated solution and the
excess, undissolved solute.
For example, a saturated solution of silver chloride is one
in which the equilibrium shown below has been established.
The equilibrium constant for solubility equilibria such as this one is called the solubility product constant, Ksp,
in this case

Applications
 Solubility equilibria are useful tools in the treatment of wastewater that may treat the municipal water.
 Specifically, selective precipitation is used to remove contaminants from wastewater before it is released
back into natural bodies of water.
 For example, phosphate ions. are often present in the water discharged from manufacturing facilities. An
abundance of phosphate causes excess algae to grow, which impacts the amount of oxygen available for
marine life as well as making water unsuitable for human consumption

8. Explain in detail the Ellingham diagrams features, observations and exceptions with graph

Ellingham Diagram
An Ellingham diagram is referred to as a graphical representation that shows the dependence of a compound
stability on the temperature. The analysis done through the Ellingham diagram helps in determining
the equilibrium temperature between the metal, its oxides and oxygen and through the process of extension
helps in predicting the reaction between a metal with sulphur, nitrogen and other non-metals.
The Ellingham diagram helps in determining the favourable conditions under which an ore will turn into its
metal form.
 21

Features of the Ellingham Diagram

It is a plot of ΔGo in kJ/mol of oxygen versus the temperature for the formation of oxides.
 The graphs of metal to metal oxide reactions for a majority of metals shows a positive slope.
 The line for the change of Gibbs energy is a straight line unless the substance does not change its state
to liquid or gas.
 When the substance changes its state, an increase in the slope on the positive side is observed.
 According to the Ellingham diagram on increasing the temperature, after a certain point, ΔG will be
zero.
 Beyond this temperature, the free energy for the formation of the oxide is positive. This leads to the
oxide being unstable which results in its decomposition into its respective metal and oxygen.
 For temperatures up to this temperature, the free energy for the formation of oxides is negative. This
leads to the oxide being stable.

Observations from the Ellingham Diagram

 Any metal that lies above another metal in the Ellingham diagram has the ability to reduce it.
 For a majority of metals, the slope for the formation of their respective oxide is found to be positive.
 Some metal oxides like HgO, MgO show a drastic change in their slope at a given temperature.
 22

Exceptions to the Ellingham Diagram

Some cases can be observed for which when the entropy is positive, the slope for the substances is downwards.
Few examples of such exceptions are:
 C (s) + O2 (g) → CO2 (g): In this reaction, a single molecule is leading to the formation of another single
molecule of gas. Hence, the entropy is null and the slope is zero which is represented by a horizontal line.
 2C (s) + O2 (g) → 2CO (g): In this reaction, a single molecule is leading to the formation of two
molecules of gas. Hence, the entropy is positive resulting in a curve that goes downwards.

Applications of the Ellingham Diagram

 Ellingham Diagram facilitates a more efficient selection of the best reducing agent for a range of ores.
 It provides a reference on how to best purify the metals and for the removal of impurities.
 By referring to the Ellingham curve for Aluminum, it was inferred that it is an efficient reducing
agent in the thermite process, aiding in the extraction of Chromium and Manganese through the reduction of
their respective oxides.
 The Ellingham Diagram is used to identify the point of equilibrium of the oxidation-reduction process.

Limitations of the Ellingham Diagram

 The kinetics of the reactions are not taken into consideration in the Ellingham Diagram.
 The diagram fails to provide complete information regarding the oxides and their formations. For
instance, if more than 1 oxide of a metal can be formed, the information for the same through the Ellingham
diagram cannot be attained.

9. Write short note on the Types of Intermolecular Forces with ex (Dipole-Dipole Interactions, Van der
Waals interactions)
INTERMOLECULAR FORCES,
 Intermolecular forces, often abbreviated to IMF, An
intermolecular force is an attractive force that arises between the
positive components (or protons) of one molecule and the
negative components (or electrons) of another molecule.
Types of Intermolecular Forces
The intermolecular forces depend on the following interactions:
1. Dipole-Dipole Interactions
Dipole-dipole interactions are attractive forces among polar
molecules. Polar molecules have permanent dipoles that are
formed due to differences in the electronegativities of the atoms that are associated with a covalent bond. The
partially positive portion of one molecule is attracted to the partially negative portion of another molecule.
Example: Dipole-dipole interactions occur in HCl molecules. Chlorine is comparatively
more electronegative than hydrogen and it, therefore, acquires a partial negative charge (whereas hydrogen
acquires a partial positive charge). The dipole-dipole interaction then takes place between the HCl molecules.
 23

2. Ion-Dipole Interactions
These interactions are similar to dipole-dipole interactions except for the fact that they arise between ions and
polar molecules. Example: When NaCl is mixed with water in a beaker, the polar H 2O molecules are attracted
to the sodium and chloride ions in the beaker.
The strength of this interaction depends on:
 The magnitude of the dipole moment
 Size of the polar molecule
 The size and charge of an ion
3. Ion Induced Dipole Interactions
In this type of interaction, a non-polar molecule is polarized by an ion placed near it. The non-polar molecules,
upon obtaining a charge, behave as induced dipoles. This interaction between an ion and an induced dipole is
known as ion-induced dipole interaction.
4. Dipole Induced Dipole Interaction
These interactions are similar to ion-induced dipole interactions. However, the differentiating factor is that non-
polar molecules are transformed into induced dipoles due to the presence of a polar molecule nearby.
5. Dispersion Forces or London Forces
It operates for a short distance and it is the weakest force. This kind of force arises due to the movement of electrons
thus creating temporary positive and negative charged regions

10. Write note on Critical constants

The three critical constants—critical pressure, critical volume and critical temperature—are very much
important in the study of gases, especially in liquefaction.
Critical temperature (Tc)
Critical temperature (Tc) of a gas is defined as the temperature above which it cannot be liquefied at any
pressure.

Critical pressure (Pc)

Critical pressure (Pc) of a gas is defined as the minimum pressure required to liquefy 1 mole of a gas
at its critical temperature.

Critical volume (Vc)

Critical volume (Vc) is defined as the volume occupied by 1 mole of a gas at its critical temperature
and critical pressure.

UNIT IV
1. Define effective nuclear charge , Shielding and explain its periodic trend
EFFECTIVE NUCLEAR CHARGE
In addition to the electrostatic forces of attraction between the nucleus and the electrons, there exists repulsive
forces among the electrons.
The repulsive force between the inner shell electrons and the valence electrons leads to a decrease in the
 24

electrostatic attractive forces acting on the valence electrons by

the nucleus. Thus, the inner shell electrons act as a shield
between the nucleus and the valence electrons. This effect is called
shielding effect.
The net nuclear charge experienced by valence electrons in the
outermost shell is called the effective nuclear charge.
It is approximated by the below mentioned equation. Zeff = Z - S
where Z is the atomic number and S is the screening constant which can
be calculated using Slater's rules
Periodic Trend
Along Period Zeff decreases along a period from left to right due to decrease in atomic size as a result of the
filling of next electron in the same shell.
Down the Group Zeff increases down the group due to an increase in the number of shells which results in an
increase in the atomic size. The nuclear charge increases, but its effect remains relatively negligible compared
to the effect of the increasing number of shells.

2. Explain penetration and of orbitals

Penetration & Shielding
Electrons are negatively charged and are pulled pretty close to each
other positive charge of a nucleus. The electrons are attracted to the
nucleus at the same time as electrons repel each other. The balance between
attractive and repulsive forces results in Shielding
The orbital (n) and subshell (ml) define how close an electron can
approach the nucleus. The ability of an electron to get close to the
nucleus is penetration.

Orbital Penetration
Penetration describes the proximity to which an electron can approach to the nucleus. In a multi-electron
system, electron penetration is defined by an electron's relative electron density (probability density) near the
nucleus of an atom.
The penetration power of an electron, in a multi-electron atom, is dependent on the values of both the shell and
subshell.
Within the same shell value (n), the penetrating power of an electron follows this trend in subshells (ml):
s>p>d>f
And for different values of shell (n) and subshell (l), penetrating power of an electron follows this trend:
1s>2s>2p>3s>3p>4s>3d>4p>5s>4d>5p>6s>4f.... and the energy of an electron for each shell and subshell goes
as follows... 1s<2s<2p<3s<3p<4s<3d<4p....

3. List the different types of molecular geometries

MOLECULAR GEOMETRIES
Molecular geometry, also known as molecular structure or conformation, is the three-dimensional arrangement
of atoms in a molecule.
 25

It includes the molecule's general shape, bond angles, bond lengths, torsional angles, and other geometrical
parameters that determine the position of each atom.
Types of molecular structure

Shape Geometry Structure Example

a simple triatomic molecule of the

Linear
type AX2; its two bonding orbitals CO2
are 180° apart.

Trigonal triangular and in one plane, with

BF3
planar bond angles of 120°.

four bonds on one central atom

Tetrahedral CH4
with bond angles of 109.5°.

five atoms around the central atom;

Trigonal three in a plane with bond angles of
PCl5
bipyramidal 120° and two on opposite ends of
the molecule.

six atoms around the central atom,

Octahedral SF6
all with bond angles of 90°.

4. Explain the variations of s, p, d and f orbital energies of atoms in the periodic table
Variations of s, p, d and f orbitals
In an atom, the energy of the s, p, d, and f orbitals increases from lowest to highest as you move up the
orbital. The s orbital has the lowest energy, while the f orbital has the highest energy (s < p < d < f).
The energy of an electron in multi-electron atoms depends on both its principal quantum number (n) and its
azimuthal quantum number (l).
Here are the orbital energies in increasing order:
1s, 2s = 2p, 3s, 3p = 3d, 4s, 4p = 4d, and 4f.
The s orbital is symmetrically spherical about the axis, and as the energy levels increase, the electrons are
located further away from the nucleus. The p-orbitals are oriented in a particular direction, and there are three
p-orbitals in a given energy level: Px, Py, and Pz. The d-orbital is composed of five orbitals: dxy, dyz, dxz, dx²-
y², and dz².
 26

Each orbital can hold a different number of

electrons:
s: 1 orbital, 2 electrons
p: 3 orbitals, 6 electrons
d: 5 orbitals, 10 electrons
f: 7 orbitals, 14 electrons

5. Discuss the definition and variation of Polarizability

POLARIZABILITY
The ability of a cation to distort an anion is known as its polarization power and the tendency of the anion to
become polarized by the cation is known as its polarizability.
Fajans' Rules
It is used to predict whether a chemical bond is
expected to be predominantly ionic or covalent, and
depend on the relative charges and sizes of the cation and
anion.
If two oppositely charged ions are brought together, the
nature of the bond between them depends upon the
effect of one ion on the other.. If the degree of polarization is quite small, an ionic bond is formed, while if the
degree of polarization is large, a covalent bond results.
Polarization power
The ability of a cation to distort an anion is known as its polarization power and the tendency of the anion to
become polarized by the cation is known as its polarizability
The polarizing power and polarizability that enhances the formation of covalent bonds is favoured by the
following factors:
Factors affecting polarisability
Size of cation
Polarisation of the anion increases as the size of cation decreases.
Size of cation decreases Covalent character increases
In a group – BeCl2
- Size of cation increases
- Covalent character decreases
- Ionic character increases
Size of anion
If the size of anion increases for a given cation, the covalent character increases
- Size of anion increases
- Covalent character increases
Ionic character decreases
Charge on cation and anion
Charge on cation increases
Covalent character increases
Ionic character decreases
 27

6. Discuss the definition, and variation of ( across the period and down the group) Atomic and ionic radii
Atomic radius of an atom is defined as the distance between the centre of its nucleus and the outermost shell
containing the valence electron.
It is not possible to measure the radius of an isolated atom directly.
Except for noble gases, usually atomic radius is referred to as covalent
radius or metallic radius depending upon the nature of bonding between the
concerned atoms.
Periodic Trends in Atomic Radius
Variation in Periods
Atomic radius tends to decrease in a period.
When move from left to right along a period, the valence electrons are added to the same shell. The
simultaneous addition of protons to the nucleus, increases the nuclear charge, as well as the electrostatic
attractive force between the valence electrons and the nucleus. Therefore atomic radius decreases along a
period.

IONIC RADIUS
It is defined as the distance from the centre of nucleus of the ion up to which it exerts its influence on
the electron cloud of the ion.
An atom can be changed to a cation by loss of electrons and to an anion by gain of electrons.
The size of a cation is smaller in comparison to the size of its corresponding atom. This results in increase in the
effective nuclear charge.

The size of an anion is greater than the size of its corresponding atom, because the number of electrons present
in the anion gets larger than the number of protons due to gain of electrons. This results in decrease in the
effective nuclear charge.
Ex: Mg2+ < Mg and Cl– > Cl
Periodic Trends in ionic radius
The ionic radius decrease moving from left to right across
any period in the periodic table.
As the valence electrons get added to the same energy
level, at the same time when the nucleus is increasing in
protons. The increasing nuclear charge attracts the
electrons strongly and keeps them close to the nucleus.
Down the group, the ionic radius of atoms increases.
As the number of electronic shells increases resulting in
an increase in the size of atom.

7. Discuss the definition, and variation of (Periodic trend) Ionization energy Electro-negativity
IONISATION POTENTIAL
It is defined as the minimum amount of energy required to remove the most loosely bound electron from the
valence shell of the isolated neutral gaseous atom in its ground state.
It is expressed in kJ/mol or in electron volts (eV).
 28

Factors Affecting Ionisation Potential

(i) Atomic size: When the size of an atom is very large the electron of the outermost orbit bound to the nucleus
by weaker attractive forces. Such an electron will be readily removed from the atom. Therefore, the value of
ionisation potential will be low.
(ii)Effective Nuclear Charge: Atomic size decreases with increase in effective nuclear charge because, higher
the effective nuclear charge stronger will be the attraction of the nucleus towards the electron of the outermost
orbit and higher will be the ionisation potential.
(iii) Shielding Effect: The electrons of internal orbits repel the electrons outermost orbit due to which the
attraction of the nucleus towards the electron of outermost orbit decreases and thus atomic size increases and
the value of ionisation potential decreases.
(iv) Stability of half filled and fully filled orbitals: The atoms whose orbitals are half-filled (p) or fully-
filled (s2, p6) have greater stability than the others. Therefore, they required greater energy for removing out
electron. However stability of fully filled orbitals is greater than that of half- filled orbitals.
(v) Penetration power: In any atom the s orbital is nearer to the nucleus in comparison to p, d and f orbitals.
Therefore, greater energy is required to remove out electron from s orbital than from p, d and f orbitals. Thus
the decreasing order of ionisation potential of s, p, d and f orbitals is as follows s >p >d>f

Periodic Trends in Ionisation Energy

In Period
Ionisation energy usually increases along a period with few
exceptions.
The valence electrons are added to same shell, at the same time
protons are added to the nucleus. This successive increase of nuclear
charge increases the electrostatic attractive force on the valence
electron and more energy is required to remove valence electron
resulting in high ionisation energy.
In a Group

Ionisation potential normally decreases on going from top to bottom in a

group because both atomic size and shielding effect increase.

ELECTRON AFFINITY
Amount of energy released when an electron is added to the
valence shell of an isolated neutral gaseous atom in its ground state to
form its anion is called electron affinity.
It is expressed in eV or kJ/mol.
Factors Affecting Electron Affinity
Effective Nuclear charge
When effective nuclear charge is more, then the atomic size less. Hence EA increases.
Atomic Size or Atomic Radius
When the size or radius of an atom increases, the electron entering the outermost orbit is more weakly attracted
by the nucleus and the value of electron affinity is lower.
 29

Shielding Effect
Shielding effect is directly proportional to atomic size and atomic size is inversely proportional to electron
affinity.
Stability of Fully-Filled and Half-Filled Orbitals
The stability of the configuration having fully-filled orbitals (p6, d10) and half-filled orbital (p) is relatively
higher than that of other configurations.
Periodic Table and Electron Affinity
In a period
In a period, generally electron affinity increases.
This is due to an increase in the nuclear charge and decrease in
size of the atoms.
Noble gases have stable ns2, np6 configuration, and the addition
of further electron is unfavourable and requires energy.
Halogens having the general electronic configuration of ns2, np5
readily accept an electron to get the stable noble gas electronic
configuration (ns2, np6), and therefore in each period the halogen
has high electron affinity. (high negative values)

In a group
As we move down a group, generally the electron affinity
decreases.
It is due to increase in atomic size and the shielding effect of inner
shell electrons.

ELECTRONEGATIVITY
Electronegativity is defined as the relative tendency of an element
present in a covalently bonded molecule, to attract the shared pair of
electrons towards itself.
The electronegativity of any given element is not a constant and its
value depends on the element to which it is covalently bound. The
electronegativity values play an important role in predicting the nature
of the bond.
Periodic Trends in Electronegativity

In a period
The electronegativity generally increases across a period from left to
right.
The atomic radius decreases in a period, as the attraction between the
valence electron and the nucleus increases. Hence the tendency to attract
shared pair of electrons increases. Therefore, electronegativity also
increases in a period.
 30

Periodic Trends in Electronegativity

In a group
The electronegativity generally decreases down a group.
Down a group the atomic radius increases and the nuclear
attractive force on the valence electron decreases. Hence, the
electronegativity decreases.
Noble gases are assigned zero electronegativity. The
electronegativity values of the elements of s-block show the
expected decreasing order in a group. Except 13th and 14th
group all other p-block elements follow the expected
decreasing trend in electronegativity.

UNIT V
1. Define Isomerism and Classification of Structural Isomerism
Structural isomerism, or constitutional
isomerism, is a type of isomerism where
isomers have same molecular formula but have
different arrangements of atoms within the
molecule.
Generally isomerism can be divided in to two
categories;
a. Structural (constitutional)
Isomerism
b. Stereo (configurational) Isomerism
Structural isomerism: Structural isomers are
compounds those have identical molecular formulae but different structural formulae
Chain Isomerism:
Chain isomers are those isomers having difference in the order in
which the carbon atoms are bonded to each other.
Functional Isomerism:
Two or more than two molecules those having the same molecular
formulae but have different functional groups are called functional
isomers

Position Isomerism:
Two or more than two molecules those having same molecular formulae but having difference in the position of
functional group on the carbon chain are called position isomers

Metamerism:
 31

Two or more than two molecules those having same molecular formulae and functional group but having
difference in the distribution of carbon atoms on either side of functional group are called metamers

Tautomerism:
This is a special kind of isomerism where both the
isomers are interconvertible and always exist in a
dynamic equilibrium to each other. Due to their
interconversion change in functional group takes
place that gives two different isomers of an organic compound. This phenomenon is called Tautomerism.

2. Define Isomerism and Classification of Stereo Isomerism

Stereoisomerism:
Stereoisomerism, the existence of isomers
(molecules that have the same numbers of the same
kinds of atoms and hence the same formula but differ
in chemical and physical properties) that differ in the
orientation of their atoms in space. There are two
kinds of stereoisomers: enantiomers and
diastereomers
Stereoisomerism can be categorized into two
categories:

 Geometrical isomerism.
 Optical isomerism.

GEOMETRICAL ISOMERISM:
Geometrical isomerism is generally observed in alkenes and cyclic compounds due to their restricted rotation
around carbon- carbon bond. The rotation about a double bond in alkene or about a single bond in a cyclic/ring
like compound is restricted.

Conditions for geometrical isomerism

 Restricted rotation around the C – C double bond.
 Two atoms or groups attached to the molecule with the
doubly bonded carbon atom must be different.
 However, it doesn't matter whether the left side groups are
the same or different on the right side
Geometrical isomers are non-mirror image of each other hence they are called diastereomers. Therefore their
physical and chemical properties are different
 32

Optical isomerism
Optical isomerism is another class of stereoisomerism. The organic compounds that exhibit optical isomerism
must have a unique ability to rotate the plane polarized light either towards left or towards right hand directions.
This unique ability is generally known as optical activity.
Condition For Optically Activity
 Molecule should contain atlest one chiral carbon An asymmetric carbon atom is that which is bonded to four
different atoms or groups.
 The molecule should not possess any kind of symmetry elements. the molecule should be dissymmetric
 It should have non superimposible mirror images called ‘enantiomers’ Then only the molecule is optically
active and rotates the plane polarized light

Conformational isomerism is a form of stereoisomerism in which the isomers can be interconverted just by
rotations about formally single bonds

3. Explain in detail the Relative- D/L Nomenclature

D/L NOMENCLATURE: (relative configuration)
The D/L nomenclature is the oldest nomenclature system for enantiomers. where the configuration of
glyceraldehyde molecule is taken as an arbitrary standard.

According to this nomenclature if in glyceraldehyde molecule the –OH group on right and –H on left, the –
CHO and –CH2OH groups being on top and bottom, respectively the molecule is designated as (+)
Glyceraldehyde and it was arbitrary given the
configuration symbol D.
The mirror image of this compound (-)
glyceraldehyde was given the configuration L.
 33

Any compound that can be prepared, or converted in to D-(+)-glyceraldehyde will belong to D series (relative
configuration), whereas, any compound that can be prepared, or converted in to L-(+)-glyceraldehyde will
belong to L series. Lactic acid obtained from D-(+)-glyceraldehyde and hence assigned D configuration

4. Absolute Configuration - R/S Nomenclature:

R/S NOMENCLATURE: (absolute configuration).
There are several drawbacks associated with the D/L nomenclature system. Hence a definite and universally
applicable nomenclature system the R/S system or Cahn-Ingold-Prelog (CIP) nomenclature was proposed..

Steps
❖ Assign the priority to the four different atoms/groups attached to a chiral centre.
❖ Priorities to the groups as per the sequence rule.
❖ The molecule is oriented in such a way that the lowest priority group is directed away to the observer.
❖ While viewing following deceasing order of priorities from highest priority to lowest priority.
❖ While viewing the atoms/groups in their decreasing order if your eyes follow the clockwise direction then
the chiral centre will have R configuration;
 whereas if your eyes follow anticlockwise direction the chiral centre will have S configuration. ❖
SEQUENCE RULE:
To assign the priorities to all four different groups/atoms
attached with the chiral centre sequence rule should be
followed.
1. The sequence of priorities is determined by their atomic
number.
2.If two or more atoms attached to the chiral centre having
same atomic number, the priorities are assigned by
comparing the atomic numbers of the next atoms attached to
each group/atom.
3. The double or triple bonded atoms are considered to be duplicate or triplicate..

5. Conformational Analysis Of Ethane

When ethane molecule rotates around carbon-carbon single bond, two extreme
conformations (one is highly stable and other is highly unstable) are obtained. The
highly stable conformation of ethane is called ‘staggered conformation’ and the
highly unstable conformation of ethane is called ‘eclipsed conformation’. In between
these two extreme conformations (i.e. staggered and eclipsed), an infinite number of
conformations are also possible.

Staggered conformation: A conformation with a 60° dihedral angle is known as staggered conformation. The
angle between the atoms attached to the front and rear carbon atom is called dihedral angle.
Eclipsed conformation: A conformation with a 0° dihedral angle is known as eclipsed conformation.
 34

In staggered conformation the atoms are located at maximum possible distance from each other hence they are
in their most relaxed spatial arrangement thus the staggered conformation is considered as the most stable
conformation; whereas, in eclipsed conformation the atoms are located at minimum distance, hence due to
repulsion between the atoms the eclipsed conformation is considered as the least stable (high energy)
conformation.
Representation of Staggered and Eclipsed Conformations,
a) the Sawhorse representation formula and,
b) the Newman representation formula.
 The Sawhorse Representation Formula
 In this projection, the molecule is viewed along the
molecular axis.
 It is then projected on paper by drawing the central C-C
bond as a somewhat longer straight line.
 The upper end of the line is slightly tilted towards the right
or left-hand side.
 The front carbon is shown at the lower end of the line,
whereas the rear carbon is shown at the upper end.
 Three lines are attached to each carbon, each corresponding to three hydrogen atoms. The lines are at a 120°
angle to one another.
:
Newman's projection formula
The molecules are observed along the connection connecting the
main carbon atoms, shown as superimposed circles in the Newman
projection formula. The remaining connections in every carbonyl
group are shown by short straight lines intersecting the centre and
circumference at an angle of 120°.

A graph plot for the energy profile for various

conformations of ethane is shown on figure. The relative
stability of various conformations of ethane is Staggered >>
Eclipsed

6. Conformational Analysis of n-Butane

n-Butane (C4H10) has three carbon-carbon single bonds
(Figure); The rotation about C2 and C3 bond will provide
the symmetrical conformations
Representation of Conformations,
a) The Sawhorse representation formula and,
 35

b) The Newman representation formula

. To study the conformational analysis of n-butane, we must

consider it as a derivative of ethane molecule,

where one hydrogen at each carbon of ethane is
replaced by methyl group (-CH3).
Various conformation of n-butane can be obtained
by rotation about C2 and C3 bond are shown in
figure:
From figure, we can see that n-butane has three
staggered conformations (I, III and V). Conformer
I, in which two methyl groups are as far as
possible, and hence is more stable than other two staggered conformers (i.e. III and V) due to difference in
steric strain, is called the anti-conformer, because conformer I, has minimum repulsive energy. Whereas other
two staggered conformers (i.e. III and V).
are called gauche conformer.

7. Write short note on Symmetry and its types

ELEMENTS OF SYMMETRY
Elements of symmetry are a simple tool to identify whether a molecule is chiral or not.
Types
(i) Simple axis of symmetry (Cn)
(ii) Plane of symmetry (σ)
(iii) Centre of symmetry (Ci)
(iv) Alternating axis of symmetry (Sn)

(i) Simple axis of symmetry (Cn):

Proper axis of symmetry or rotational axis of symmetry (Cn): If a
chemical entity rotating about an axis through an angle of 360°
coincides with itself n times, the axis is referred to as the proper
rotational axis of order n or n-fold simple axis of symmetry
Water molecule has C2 (two fold axis of symmetry) whereas
chloroform has C3 axis of symmetry.

(ii) Plane of symmetry (σ):

 36

It is defined as ‘when a plane that devised a molecule or object in to two equal halves which are related to
object and mirror image is known as plane of symmetry. It is represented by σ.
Plane of symmetry in Tartaric acid

(iii) Centre of symmetry (Ci):

A molecule has a centre of symmetry when, for any atom in the molecule,
an identical atom exists diametrically (diagonally) opposite to this centre
and at equal distance from it. An isomer of 1,3-dichloro-2,4-
dibromocyclobutane has a centre of symmetry
(iv) Alternating axis of symmetry (Sn):

8. Explain the Synthesis of a Drug molecule with equations (Paracetamol, Asprin)

Preparation of Aspirin
Principle: The chemical name of aspirin is acetyl salicylic acid
Salicylic acid undergoes o-acetylation with acetic anhydride in the presence of conc. H2SO4 to give o-acetyl
salicylic acid.

Procedure
Add 3 g of salicylic acid to the clean R.B. flask. Mix 5 ml of acetic anhydride and 5 ml of acetic acid in a
beaker, add this mixture to the R.B. flask containing salicylic acid. Heat the mixture for about 20 min. on the
water bath. Then add this hot mixture in to the ice cold water taken in a beaker and stir vigorously. Crude solid
sample of aspirin separates out. Filter solid aspirin using funnel. The yield is about 3.5 g.
Uses
 Aspirin is extensively used as an antipyretic, analgesic, anti-inflammatory drug,
 As a medicine which prevents heart attack by checking clotting in arteries.
 , As a pain killer in treatment of arthritis and minor injuries
 It reduces fever.
 37

Preparation of Paracetamol
Principle: Paracetamol, also known as acetaminophen or APAP,
p-aminophenol, , is treated with acetic anhydride to form acetaminophen (p-acetamidophenol),.

Procedure:
2.0 g of 4-aminophenol, 20 ml of distilled water and 3 ml of acetic anhydride are taken in a round bottom flask
fitted with a reflux condenser. The mixture is refluxed for 15 mins until the reaction mixture becomes colorless.
The hot liquid is poured on crushed ice with stirring in a beaker. Filter the colorless crystalline solid, wash it
with cold water and then dried.
Uses
To treat pain and fever.
9. Explain the Different types of organic reactions with example
Different types of organic reactions
Substitution reactions
Addition reactions
Elimination reactions
Oxidation and reduction reactions

Substitution reaction (Displacement reaction)

In this reaction an atom or a group of atoms attached to a carbon atom is replaced by a new atom or a group of
atoms.
Based on the nature of the attacking reagent, this reactions can be classified as
i) Nucleophilic substitution,
ii) Electrophilic substitution,
Nucelophilic substituion:
Incoming nucleophile(meaning nucleus loving, the positive center of an atom) replaces the existing group
(leaving group).
A nucleophileis a Lewis base that seeks a positive center replaces the existing group.

SN1 reaction and the SN2 reaction, where S represents chemical substitution, N represents nucleophilic, and the
number stands for the kinetic order of a reaction.

The electrophilic substitution

The electrophilic substitution reaction involves the electrophiles. Electrophiles are those which donate a pair of
electrons in the formation of a covalent bond. The Electrophilic reactions occur mostly with the aromatic
compounds. Some examples of species of electrophiles include hydronium ion (H3O+), halides of hydrogen
such as HCl, HBr, HI, sulphur trioxide (SO3), the nitronium ion (NO2+), etc.
 38

Addition Reaction:
An addition reaction is a chemical reaction wherein two or more reactants come together to form a larger single
product.

Types of Addition Reactions

1. Electrophilic Addition reactions
2. Nucleophilic Addition reactions

Electrophilic addition: In organic chemistry, an electrophilic addition reaction is an addition reaction where
a π bond is broken and two new σ bonds are formed. The substrate of an electrophilic addition reaction must
have a double bond or triple bond.

Nucleophilic addition:
A nucleophilic addition reaction is an addition reaction where a chemical compound with an electron-deficient
or electrophilic double or triple bond, a π bond, reacts with a nucleophile which is an electron-rich reactant with
the disappearance of the double bond and creation of two new single, or σ, bonds.

Elimination reaction
 39

A type of organic reaction in which two substituents are removed from a molecule in either a one or two-step
mechanism.

Oxidation and reduction reactions

 Organic reductions or organic oxidations are redox reactions that take place with organic compounds.
 The relevant criterion for organic oxidation is gain of oxygen and/or loss of hydrogen.
 Classical oxidations include oxidation of alcohols to aldehydes.
 Classical reductions include alkene reduction to alkanes and
 Some important oxidizing agents are: Jones reagent, Collins reagent, alkaline KMnO4, Pyridinium
chlorochromate (PCC), Pyridinium dichromate (PDC) etc.
 Some important reducing agents are: LiAlH4, NaBH4, Hydrogenation, Borane, etc.