Unit 1:

Huckel’s rule of aromaticity:

A ring-shaped cyclic molecule is said to follow the Huckel rule when the total
number of pi electrons belonging to the molecule can be equated to the formula
‘4n + 2’ where n can be any integer with a positive value (including zero).

Criteria for aromaticity:

 The molecule is cyclic (a ring of atoms)
 The molecule is planar (all atoms in the molecule lie in the same plane)
 The molecule is fully conjugated (p orbitals at every atom in the ring)
 The molecule has 4n+2 π electrons (n=0 or any positive integer)

Aromatic vs anti-aromatic vs non-aromatic

In the quantum mechanical model of the atom, a nodal plane is a region around
the nucleus where the probability of finding an electron is zero or almost zero.
The number of nodal planes in an orbital is equal to the azimuthal quantum
number

<----- azimuthal
Quantum numbers

Example:

So in total, we have 11 nodal planes

Factors influencing CFSE:
* Nature of ligand
* Oxidation state of metal ion
*Coordination number
*Steric effects
*Geometry of complex

The electromagnetic spectrum is a range of frequencies, wavelengths and

photon energies covering frequencies from below 1 hertz to above 10^25 Hz,
corresponding to wavelengths which are a few kilometers to a fraction of the
size of an atomic nucleus in the spectrum of electromagnetic waves.

Periodic
properties:
Outer ECs:
Trends:
1.Atomic size: increases down grp as more shells being added
Decreases from left to right in period since atomic no increases
2.Ionic size: Cation: size decreases than parent element (since no of electrons
decrease)
Anion: size increases than parent element (since no of electrons increase)
3.Effective nuclear charge:
Actual amount of positive (nuclear) charge experienced by an electron in a
multi-electron atom. The term "effective" is used because the shielding effect of
negatively charged electrons prevent higher energy electrons from experiencing
the full nuclear charge of the nucleus due to the repelling effect of inner layer.
decreases down grp
Increases from left to right in period
4.Ionisation energy: decreases down group, increases from left to right along a
period
5.Electron affinity or electron gain enthalpy:
Decreases down grp. Increases from left to right across period
6.Electronegativity: Decreases down grp, increases from left to right across
period
Fluorine is the most electronegative of the elements, whereas
Francium is the least electronegative.
7.Electropositivity: Increases down grp, decreases from left to right across
period

Pauling’s electronegativity scale: F>O>[N=Cl (approx..)]

An atom with high electronegativity has high ionisation potential
Electron gain enthalpy trend in halogens: F<Cl>Br>I
When an electron is added in the valence shell, then Energy is released

HSAB PRINCIPLE:

Linkage of ambidentate ligands to metal atoms:

It is one of the important applications of the HSAB principle. The SCN^- ligand
is an ambidentate ligand and can be S-bound to metal (M-SCN) and referred to
as thiocyanate or can be N-bound to metal (M-NCS) and is referred to as
isothiocyanate. The choice among S-bound or N-bound is decided by soft or
hard acid-base behavior. S is a comparatively soft base than N atom. Hence soft
metal ions are S-bound while hard metal ions are N-bound.
1) SCN^- bonds through sulfur atom (soft base) when bonded to Pt2+, a soft
acid. It bonds through nitrogen atom (a hard base) when linked to Cr3+, a hard
acid.
2) When Fe2+ reacts with SCN^- a bright red [Fe(SCN)]+ ion is formed,
whereas Cr3+ forms [Cr(NCS)]2+.
Reason: Fe2+ is a borderline acid and is S-bound. Whereas Cr3+ is hard acid
and prefers to be N-bound.
3) The molecule (CH3)2NCH2PF2 would bond to BF3 through N whereas it
would bond to BH3 through P.
Reason: BF3 is a hard acid and prefers to bind with N atom - a hard base.
Whereas, BH3 is a soft acid and preferentially bonded to soft base, P atom.
In order to determine which direction is more favored in a reaction, we have to
check the stability of the compounds. A stable compound is formed between a
hard acid and a hard base as well as from a soft acid and a soft base.
Species having strong tendency to accept electrons and form ionic bond with
base--Hard acids

UNIT 5:

Why is XPS a more qualitative than quantitative technique?

A: XPS not only shows what elements are present, but also what other elements
they are bonded to. The technique can be used in line profiling of the elemental
composition across the surface, or in-depth profiling when paired with ion-beam

etching.
It can identify the elements that exist within a material (elemental composition)
or are covering its surface, as well as their chemical state, and the overall
electronic structure and density of the electronic states in the material.
Therefore, XPS is more qualitative than quantitative.

Give the number of electrons and best suitable pressure required for XPS
measurement.
A: XPS requires high vacuum (residual gas pressure p ~ 10−6 Pa) or ultra-high
vacuum (p < 10−7 Pa) conditions
The number of electrons needed for XPS analysis is determined by the element
of interest and the specific core level being investigated.
For example, Carbon (C): In XPS, one might analyze the C 1s core level, which
involves the removal of a single electron from the 1s orbital of a carbon atom.
Oxygen (O): For oxygen, the O 1s core level is often studied, involving the
removal of an electron from the 1s orbital of an oxygen atom.

What is the principle of XPS?

A: Photoelectric effect (explain)

Give only schematic diagram for XPS instrumentation.

A:

What are the merits and demerits of XPS analysis?

A:

Define the terms: Binding energy and Work function in XPS analysis. A:
binding energy is the energy required to remove an electron from its orbit
around the nucleus. The strength of the binding between electrons and the
nucleus is quantified by the ionization energy, which is essentially the negative
of the binding energy.
Work function represents the minimum amount of energy required to remove an
electron from the surface of a material and liberate it into free space. The work
function(φs) is closely related to the binding energy of electrons in a material.
K.E. = hν – B.E. - φs

What are the applications of XPS? [Any two]

A:

Define Miller indices with examples

A: Miller introduced a set of 3 numbers to designate a plane in a crystal. This
set of 3 numbers is called Miller Indices. The orientation of a plane in a crystal
is usually described in terms of their intercepts on the 3 axes.
For example, a plane ABC in has intercepts of 2 axial units on x and y axes, and
1 axial unit on z axis. In other words, the numerical parameter of this plane
becomes (2,2,1). Miller suggested that a plane’s orientation is best described by
the reciprocal of these intercepts.
Hence, the miller indices become (1/2,1/2,1) or (1,1,2).

Points from MCQs:

1. In fiber reinforced composites longitudinal strength is mainly influenced
by Fiber strength
2. In fiber reinforced composites Matrix fails last
3. Energy per unit volume (unit Nm/m^3 = N/m^2) has the same S.I. unit as
that of modulus of elasticity(N/m^2)
4. Bulk modulus: inverse of compressibility
5. Volumetric stresses cause change in density, as long as force acts on the
body
6. The area under the stress-strain curve represents toughness
7. The continuous phase of a composite material is known as its matrix
phase
 8. Fiber composite:

Laminate composite:

Sandwich panel composite:

9.Carbon fibres produced from thermal degradation of polyacrylonitrile (PAN)

Process: Heating-Carbonization-Graphitization
10. The energy required to remove an electron from the highest occupied atomic
orbital is known as Ionization energy
11. X-ray diffractometers are not used to identify the physical properties of
liquids
12. In XPS, the primary and secondary beams consist of X-ray photon, electron
respectively
12.1. In the hemispherical electron analyser of XPS, Number of electrons
striking the detector is determined and plotted as a function of binding energy
13.The scattering of waves in Bragg’s law experiment is due to Rayleigh
scattering
14. For destructive interference to take place, the path difference between the
two waves should be nλ
15. In Bragg’s equation [nλ = 2.d.sinθ], θ is the angle between parallel lattice
surfaces distance apart and incident rays
16. In stress vs strain graph (stress- x axis, strain-y axis), slope gives modulus of
elasticity
Material with max slope has max modulus of elasticity (since graph similar to
y=mx [stress= E* strain])
17. In the below stress strain curve, steeper the slope larger would be the
Young’s modulus, thus it will be difficult to draw wires from such material and
it will be less ductile. Thus, material A is stronger compared to B, whereas B is
more ductile compared to A.

UNIT 4:
 Points from MCQs:
 Phenolic resins are thermosetting polymers
 Polystyrene, polyolefins and nylons are thermoplastics that can be
softened using heat
 Monofunctional polymers (functionality=1) unsuitable for condensation
polymerization
 Cross linked polymer: low solubility
 Cohesion: action or property of like molecules sticking together, being
mutually attractive, which is lowest in rubbers
 Fibres’ tensile strength range: highest (20k to 150k)when compared with
polymers
 Isotactic- high crystallinity due to steric regularity which results in close
packing
 Elastomers are polymers that have rubber like elastic properties. The
polymer chains are held together by the weakest intermolecular forces,
which facilitate the stretching of the polymer.
Eg: Buna-S, Buna-N, Neoprene
 Polyamide fibres (like nylon)- intermolecular force: hydrogen bonding
 Polyester (Dacron, terylene) and polyacrylonitrile(orlon) fibres-
intermolecular force: dipole-dipole interactions
 Acrilan is a fibre of polyacrylonitrile. It forms strong intermolecular
bonds through dipole-dipole interactions between the carbonyl and cyano
groups.
 Increasing Order of intermolecular forces: Elastomer(like Buna-N)<
Thermoplastic( like polythene, polystyrene)< Fibres (like nylon-6,6)
 Molecular masses of polymers are expressed as an average
 Polymeric molecules do not have a definite crystalline structure
 The polymer absorbs water and swells in size.
 The impact strength is measured as the toughness.
 The neighbouring polymeric chains in thermosets are held together by
covalent bond
 Epoxy, vulcanised rubber, Bakelite are some of the examples of
thermosets.
 The advantage of using conducting polymers in place of metals is their
light-weight property
 An example for semi synthetic polymer is Rayon
  Aramid fibers are used for Bullet proof jackets
 In place of natural rubber butyl rubber can be used
 Polytetrafluoroethylene (PTFE)- insulator and lubricant
 Haemodialysis tubes are made with Polyurethane intermediate
 Organic solvent containers are made with Polypropylene
 Glass transition temperature (Tg) for Nylon-6 is 50°C, which is higher
than polyethylene due toInter-molecular hydrogen bonding
 An example of polymer with ester linkage is Polyethylene Terephthalate
 For thermoplastics the process of heat softening, moulding and cooling to
rigidness be repeated

Notes from MCQs:

1.Natural rubber:
*Trade name for natural polyisoprene
*Isoprene combined with impurities and water.
*Also known as India rubber.
*Processed from a liquid known as rubber latex.
*High strength and possesses good tear and abrasion resistance.
*Easily attacked by solvents and gasoline, and also possesses low hysteresis.
2.Buna-N:
*Synthetic rubber composed of acrylonitrile and butadiene.
*Commonly known as NBR, Krynac, or Europrene.
* This rubber is used in O-rings and hoses.
3.Unvulcanized natural rubber:
*Tough and elastic material which softens on heating.
*Becomes tacky at 30 degree C and hardens at around 5 degree C.
*This rubber oxidizes to a sticky mass when out in the sun.
4.Fillers can be classified as either reinforcing fillers or inactive fillers.
Carbon black and synthetic white fibers based on silica and alumina are
examples of reinforcing fillers.
Talc, barium sulfate, chalk, and China clay are examples or inactive fillers.
5.
UNIT 3:
Nucleophilic vs electrophilic substitution:

Points from MCQs:

The hybridisation and geometry of the carbocation intermediate in SN1 reaction
is sp2, trigonal planar
In Newmann projection for ethane in the staggered conformation, the dihedral
angle for the C-H bonds is 60 degrees
E2 reaction not favoured at low temperatures
LiAlH4: epoxides to alcohols, nitriles and amides to amines, alkyl halides to
alkanes

Reactivity of halogen acids: HI>HBr>HCl>HF

Water molecule has C2 axis of symmetry