SRM INSTITUTE OF SCIENCE AND TECHNOLOGY 

FACULTY OF ENGINEERING AND TECHNOLOGY 

DEPARTMENT OF CHEMISTRY 
18CYB101J-CHEMISTRY 
PART-B  
3 Mark Module Wise 
Module-1 
1. What is the Physical significance of Wave function?
The wave function ψ associated with a moving particle is not an observable quantity and does
not have any direct physical meaning. It is a complex quantity. The complex wave function can
be represented as ψ(​x, y, z, t​) = ​a​ + i​b​ and its complex conjugate as ψ*(​x, y, z, t​) = ​a​ – i​b​.

2. Explain the term wave function?

A ​wave function​ is defined to be a ​function​ describing the probability of a particle's quantum
state as a ​function​ of position, momentum, time, and/or spin. ​Wave functions​ are commonly
denoted by the variable Ψ. A ​wave function​ may be used to describe the probability of finding
an electron within a matter ​wave​.

3. Define Eigen value and Eigen function?

A mathematical operation on a function if it gives any constant multiplied with the function itself
then, the function is eigen function for corresponding operator and the constant value obtained is
called eigen value. ​For example energy, you operate on the wavefunction with the ​quantum
mechanical operator​ associated with that parameter. The operator associated with energy is
the ​Hamiltonian​, and the operation on the wavefunction is the ​Schrodinger equation​.

4. Give any two applications of Schrodinger wave equation.

Schrodinger equation gives us a detailed account of the form of the ​wave functions​ or probability
waves that control the motion of some smaller particles. The equation also describes how these
waves are influenced by external factors. Moreover, the equation makes use of the energy
conservation concept that offers details about the behaviour of an electron that is attached to the
nucleus.
Besides, by calculating the Schrödinger equation we obtain Ψ and Ψ2, which helps us determine
the quantum numbers as well as the orientations and the shape of orbitals where electrons are
found in a molecule or an atom.

5. Write down the one-dimensional Schrodinger time independent wave equation and
the same for a free particle.

6. What is the Normalization process and give a normalized wave function for an
electron in one dimensional potential well of length “a” meter.
 7. What is the Heisenberg uncertainty principle?
Uncertainty principle​, also called ​Heisenberg uncertainty principle​ or
indeterminacy ​principle​, statement, articulated (1927) by the German physicist
Werner ​Heisenberg​, that the position and the velocity of an object cannot both be measured
exactly, at the same time, even in theory.
∆X × ∆p ≥ h/​4​πh​
Where,
∆X – uncertainty in position
∆p – uncertainty in momentum
H – planck's constant

8. Give the plots of radial wave functions for hydrogen atoms.

The solutions to Schrödinger's equation for atomic orbitals can be expressed in terms of spherical
coordinates: r, θ, and ϕ. For a point (r,θ,ϕ), the variable r represents the distance from the center
of the nucleus, θ represents the angle to the positive ​z​-axis, and ϕ represents the angle to the
positive ​x​-axis in the ​xy​-plane.
Because the atomic orbitals are described with a time-independent potential ​V​, Schrödinger’s
equation can be solved using the technique of ​separation of variables​, so that any wavefunction
has the form:
 Ψ(r,θ,ϕ)=R(r)Y(θ,ϕ)
where R(r) is the ​radial wave function​ and Y(θ,ϕ) is the ​angular wave function​:
Y(θ,ϕ)= Φ (θ)Φ(ϕ)
Each set of quantum numbers, (n, l, ml), describes a different wave function.

9. What is the significance of angular wave function?

The ​angular wave function​ describes the spherical harmonics of the electron's motion. Because
orbitals are a cloud of the probability density of the electron, the square modulus of the ​angular
wave function​ influences the direction and shape of the orbital.

10. What is Linear Combination of Atomic Orbitals (LCAO)? Give the wave function
equations for the formation of molecular orbitals by the combination of atomic
orbitals?
The Linear combination of atomic orbitals which is also known as LCAO is an approximate
method for representing molecular orbitals. It’s more of a superimposition method where
constructive interference of two atomic wave functions produces a bonding molecular orbital
whereas destructive interference produces non-bonding molecular orbital.
Conditions to be satisfied:
The conditions that are required for a linear combination of atomic orbitals are as follows:
● Same Energy of combining orbitals – ​The combining atomic orbitals must have same
or nearly same energy. This means that the 2p orbital of an atom can combine with
another 2p orbital of another atom but 1s and 2p cannot combine as they have appreciable
energy differences.
● Same symmetry about the molecular axis – ​The combining atoms should have same
symmetry around the molecular axis for proper combination, otherwise,
the ​electron​ density will be sparse.
For e.g. all the sub-orbitals of 2p have the same energy but still, the 2p​z​ orbital of an atom
can only combine with a 2p​z orbital
​ of another atom but cannot combine with 2p​x​ and
2p​y​ orbital as they have a different axis of symmetry.
In general, the z-axis is considered as the molecular axis of symmetry.
 ● Proper Overlap between the atomic orbitals – ​The two atomic orbitals will combine to
form molecular orbital if the overlap is proper. Greater the extent of overlap of orbitals,
greater will be the nuclear density between the nuclei of the two atoms.

11. Differentiate bonding and antibonding molecular orbital.

Bonding molecular orbital Anti Bonding molecular orbital

Molecular orbitals formed by the additive Molecular orbitals formed by the subtractive effect
effect of the atomic orbitals is called bonding of atomic is called anti-bonding molecular orbitals
molecular orbitals

Probability of finding the electrons is more in Probability of finding electrons is less in antibonding
the case of bonding molecular orbitals molecular orbitals. There is also a node between the
anti-bonding molecular orbital between two nuclei
where the electron density is zero.

These are formed by the combination of + and These are formed by the overlap of + with – part.
+ and – with – part of the electron waves

The electron density, in the bonding molecular The electron density in the antibonding molecular
orbital in the internuclear region, is high. As a orbital in the internuclear region is very low and so
result, the nuclei are shielded from each other the nuclei are directly exposed to each other.
and hence the repulsion is very less. Therefore the nuclei are less shielded from each
other.

The bonding molecular orbitals are The corresponding anti-bonding molecular orbitals
represented by σ, π, δ. are represented by σ​∗​ , π​∗​, δ​∗​.

12. Give the differences between atomic and molecular orbitals.

Differences between atomic orbital and molecular orbital are as follows.
Atomic orbital:
A region where there occurs a high probability of finding an electron in an atom is known as
atomic orbital.
An electron cloud leads to the formation of atomic orbitals around the atom.
Single nucleus affects the electron cloud.
Atomic orbitals are monocentric because they are found around a single nucleus.
Molecular orbital:
A region where there is the highest probability of finding an electron in a molecule is known as
molecular orbital.
When fusion of atomic orbitals that have nearly the same energy take place then it tends to the
formation of molecular orbitals.
In molecular orbitals, two or more nuclei affect the electron cloud.
Since, molecular orbitals are found around different nuclei. Hence, they are polycentric.

13. What is s-s orbital overlapping? Give examples.

When two half filled s - orbitals of two different atoms containing unpaired electrons with
opposite spin overlap with each other it is called as s-s overlap.example, formation of Hydrogen
molecule .

14. Give the Molecular orbital diagram for Carbon Monoxide molecule {N.B: Only the
diagram is required}and calculate its bond order.
Molecular Orbital diagram of Carbon monoxide molecule (CO):
Total electrons:6+8 =14
CO =σ1s​2​,σ*1s​2​,σ2s​2​,σ*2s​2​, σ2px​2​, π2py​2​= π2pz​2​.
Nb=10
Na=4
B.O =0.5 (Nb-Na)
B.O=0.5(10-4)
B.O= 3

 
15. Draw the shape of Molecular Orbitals obtained by overlap of s-p orbitals.
● To draw the shape of molecular orbitals obtained by overlapping of s and p orbital, the shape of
the s orbital and p orbital must be drawn first.
● The​ 's' orbital​ is ​spherical​ and can hold a maximum of ​two electrons​ in it.
● On the other hand, '​p' orbital ​is ​in shape in which two circles are overlapping each other​ and it
can hold a maximum of ​six electrons​.
● When these two orbitals overlap each other it leads to the formation of sigma bonding and gives
structure in which both the 's' and 'p' orbitals joined together.
● The shape of s orbital, p orbital and molecular orbitals obtained by overlap are given in the
attachment.

16. What is p-p orbital overlapping? Give only the molecular orbital diagram taking an
example.
The mutual ​overlap​ between two half-filled p-orbitals of two atoms is called ​p-p overlap​. So the
covalent bond formed is called a ​p-p​ bond. The formation of such a bond is also called
axial ​overlapping​. The two 'p' orbitals ​overlap​ each other when they acquire minimum potential
energy.
17. Give the type of overlapping that the following molecules undergo? i. H2 ii. O2 iii.
HF
i. H​2 ​– S-S Overlapping
ii. O​2 –​ S-P Overlapping
iii. HF – S-P Overlapping

18. Calculate the bond order for i. Hydrogen molecule ii. CO and iii. He
i. Hydrogen molecule – 1
ii. Carbon monoxide – 3
iii. Helium - 0

19. Give a neat sketch on five d-orbitals.

20. Give the splitting pattern of d-orbitals in Oh complexes in the presence of ligands.
 21. What is CFSE? Give the formula for calculating it in Oh complexes.
The ​crystal field stabilization energy​ (​CFSE​) is the stability that results from placing a
transition metal ion in the ​crystal field​ generated by a set of ligands.
[Co(H​2​O)​6​2+​] contains a d​7​ metal ion with a weak field ligand. This complex is known to
be high spin from magnetic susceptibility measurements, which detect three unpaired electrons
per molecule. Its orbital occupancy is (t​2g​)​5​(e​g​)​2​.
We can calculate the CFSE as -(5)(2/5)Δ​O​ + (2)(3/5)Δ​O​ = -4/5 Δ​O​.

22. What is Huckel’s rule of aromaticity? Give an example.

According to ​Huckel's rule​, all planar aromatic compounds must have [4n+2] pi-electrons
where n is an integer (i.e. n= 0, 1, 2, 3, 4…etc.). This ​rule​ estimates whether a planar ring
compound will possess aromatic properties or not.

23. Compare Non-aromatic with Anti-aromatic compounds.

Aromatic​ molecules are cyclic, conjugated, have (4n+2) pi electrons, and are
flat. ​Antiaromatic​ molecules are cyclic, conjugated, have (4n) pi electrons, and are
flat. ​Non​-​aromatic​ molecules are every other molecule that fails one of these conditions.
24. What is HOMO and LUMO in Benzene?

25. What is HOMO and LUMO for 1,3-butadiene molecules?

 26. Calculate CFSE for high spin octahedral complexes having d5, d6 and d7
configurations.

27. What is meant by a nodal plane? Explain with an example.

A ​plane​ passing through the nucleus on which the probability of finding electron is zero, is
called a ​nodal plane​. The number of ​nodal planes​ in an orbital is equal to azimuthal quantum
number(l). Only option C has value l=1. Hence, ​nodal plane​ is found in L shell and p orbital.
28. Identify aromatic, non-aromatic and anti-aromatic compounds using Huckel’s rule
from the following:

a. Anti aromatic
b. Aromatic
c. Non aromatic
d. Aromatic

29. Based on Huckel’s rule, justify which of the following are aromatic, non aromatic
and antiaromatic.

a. Non aromatic
b. Aromatic
 c. Anti aromatic
d. Aromatic

30. Calculate CFSE for [Fe(CN)6] 3- and [CoF6] 3- ions.

In [Fe(CN)6​]4−, iron has 3d6,4s2 system in ground state but in excited state it loses two electrons
in the formation of ions and two electrons from 4s, so thus Cobalt gets 3d6 configuration. Now it
is of low spin complex due to CN ligands so all 6 electrons will go to t2g​ orbitals. and 0 electrons
will be in eg​ orbital. By applying formula,
Δ = no. of electrons in t2g​​⋅​(−0.4)+ no. of electrons in eg​(0.6)
= 6(−0.4)+0(0.6)
= −2.4Δ0​
In [CoF6​]3−, cobalt has 3d7,4s2 system in ground state but in excited state it loses three electrons
in the formation of ions and two electrons from 4s and one from 3d orbital so thus Cobalt
gets 3d6 configuration. Now it is of high spin so 4 electrons go to t2g​ orbital and 2 electrons go
to eg​ orbital. By applying formula,
Δ = no. of electrons in t2g​​⋅​(−0.4)+ no. of electrons in eg​(0.6)
= 4(−0.4)+2(0.6)
=−1.6+1.2
= −0.4 Δ0​
Module-2 
31. Give any two factors that influence crystal field splitting in octahedral 
complexes. 
The factors which influence the splitting in octahedral complexes are 
● the nature of the metal ion. 
● the metal's oxidation state. A higher oxidation state leads to a larger 
splitting relative to the spherical field. 
● the arrangement of the ligands around the metal ion. 
● the coordination number of the metal (i.e. tetrahedral, octahedral...) 
● the nature of the ligands surrounding the metal ion. The stronger the 
effect of the ligands then the greater the difference between the high 
and low energy ​d​ groups. 
 
32.  What  is  Pairing  energy (P)? Give the relation between crystal field splitting 
in octahedral complexes (ΔO) and pairing energy (P). 
Pairing  energy,  P,  is  the  energy  required  to  place  two electrons in 
the  same  orbital.  If  the  crystal  field  splitting  (Δ)  is  small  because  of 
weak-bonding  ligands,  then  the  pairing  energy  will  be  larger,  and  the 
complex will be high-spin. If the crystal field splitting (Δ) is large because 
of  strong-bonding  ligands,  then  the  pairing  energy  will  be  smaller,  and 
the complex will be low-spin. 
 
33. Give the splitting pattern of d-orbitals in Td complexes in the presence of 
ligands. 
In  a  tetrahedral  crystal  field  splitting,  the ​d​-orbitals  again  split  into 
two  groups,  with  an  energy  difference  of ​Δ​tet.  The  lower  energy  orbitals 
​

will  be ​d​z2​  and ​d​x2​ -y2​ ,  and  the  higher  energy  orbitals  will 
​ ​
​
​

be ​d​xy, ​ ​d​xz and 
​ ​d​yz -
​ opposite to the octahedral case. 

 
34.​ ​Give the formula for calculating CFSE in Td complexes. 
  

 
35. Why does TD geometry favours to form High spin rather low spin 
complexes? 
In  a  tetrahedral  complex, Δ​t​Δt is  relatively  small  even  with  strong-field 
ligands  as  there  are  fewer  ligands  to  bond  with.  It  is  rare  for  the Δ​t​Δt of 
tetrahedral  complexes  to  exceed  the  pairing  energy.  Usually,  electrons  will 
move  up  to  higher  energy  orbitals  rather  than  pairs.  Because  of  this, ​most 
tetrahedral complexes are high spin. 
 
36. What is a spectrochemical series? Mention its importance. 
 The ​spectrochemical  series​ is  a  list  of  ligands  (attachments  to  a metal 
ion)  arranged  in  order  of  their  field  strength.  The  order  of  common  ligands 
according to their increasing ligand field strength. 
The  ligands  cyanide  and  CO  are  considered  strong-field  ligands  and  the 
halides  are  called weak-field ligands. Ligands such as water and ammonia are 
said to produce medium field effects. 
 
37.  Calculate  CFSE  for  high  spin  Td  complexes  having  d5​   ,  d6​   ,  d7​   ,  and  d8​  
configurations. 

 
 
 
 
38.  Calculate  the  magnetic  moment  value  for  the  following  complexes  and 
predict whether paramagnetic or diamagnetic.  
i. Low spin Oh complex with d7​ and  ​

t​2g5​ eg2​ - paramagnetic 

​
​ ​

ii. High spin Td complex with d4​ configurations. 

​

eg4​ t​2g0​ - diamagnetic 

​
​
​
39. Classify the following as high spin or low spin complexes and calculate the 
magnetic moment of the complexes.  
i. [CoF​6]3- ​ ​

t​2g4​ eg2​ - paramagnetic  

​
​ ​

ii. [NiCl​4]2-​   ​

eg2​ t​2g2​ - paramagnetic  

​
​
​

iii. [Fe(CN)​6]3-​    ​

t​2g6​ eg0​ - diamagnetic 

​
​ ​

iv. [CoCl​4]2-  ​ ​

eg2​ t​2g2​ - paramagnetic  

​
​
​

 
40. What is the electromagnetic spectrum and give its different regions? 
Electromagnetic  spectrum,  ​the  entire  distribution  of ​electromagnetic 
radiation​ according  to ​frequency​ or ​wavelength​.  Although  all  electromagnetic 
waves  travel  at  the ​speed  of  light​ in  a  vacuum,  they  do  so  at  a  wide  range  of 
frequencies, wavelengths, and ​photon​ energies.  
The  electromagnetic ​spectrum​ ​comprises​ the  span  of  all  electromagnetic 
radiation  and  consists  of  many  subranges,  commonly  referred  to  as portions, 
such as visible light or ultraviolet radiation. The various portions bear different 
names  based  on  differences  in  behaviour  in  the  emission,  transmission, 
and ​absorption​ of  the  corresponding  waves  and  also  based  on  their  different 
practical  applications.  There  are  no  precise  accepted  boundaries  between any 
of these ​contiguous​ portions, so the ranges tend to overlap. 
  
 
41. What is the significance of the selection rule in spectroscopy? 
A ​selection  rule​ describes  how  the probability of transitioning from one 
level  to  another  cannot  be ​zero​.  It  has  two  sub-pieces:  a ​gross  selection 
rule​ and  a ​specific  selection  rule​.  A  gross  selection  rule  illustrates 
characteristic  requirements  for  atoms  or  molecules  to display a spectrum of a 
given kind, such as an IR spectroscopy or a microwave spectroscopy. Once the 
atom  or  molecules  follow  the  gross  selection  rule,  the  specific  selection  rule 
must  be  applied  to  the  atom  or  molecules  to  determine  whether  a  certain 
transition in quantum number may happen or not. 
Selection  rules  specify  the  possible  transitions  among  quantum  levels 
due to absorption or emission of electromagnetic radiation. 
 
42. What are the criteria for a molecule to absorb in the Microwave region? 
During  a  transition,  the  rotational  quantum  number  must  change  by  1 
unit only, i.e. ​Δ​J​ = ±1 (angular momentum is conserved)​. 
In  other  words,  only  transitions  between  neighbouring  energy levels are 
possible. 
 
43. Give examples for microwave active and inactive molecules. 
Gross  Selection  Rule:  molecules  with  permanent  dipoles  are  microwave 
active (the molecule must be polar), e.g., heteronuclear diatomic - HCl, CO, NO, 
etc. 
Homonuclear diatomics are microwave inactive (e.g., O​2, N​2, etc.) 
​ ​

In other words, a dipole must be present in the molecule for you to get a 
rotational spectrum. 
 
44. Write a short note on the selection rule for Rotational (microwave) 
spectroscopy? 
A  photon  contains  one  unit  of  angular  momentum, so when it interacts 
with  a  molecule  it  can  only  impart  one  unit  of  angular  momentum  to  the 
molecule.  This  leads  to  the  selection  rule  that  a  transition  can  only  occur 
between  rotational  energy  levels  that  are  only  one  quantum  rotation  level  (J) 
away from another. 
ΔJ = ±1 
The transition moment integral and the selection rule for rotational transitions 
tell if a transition from one rotational state to another is allowed. 
 
45. What are allowed and forbidden transitions in spectroscopy? 
Selection rules, accordingly, may specify “allowed transitions,” those that 
have a high probability of occurring, or “forbidden transitions,” those that have 
minimal or no probability of occurring. 
 
46. Define Hooke’s law and give its significance in IR spectroscopy. 
Hooke's Law states: 
● The vibrational frequency is proportional to the strength of the spring; 
the stronger the spring, the higher the frequency. 
● the vibrational frequency is inversely proportional to the masses at the 
ends of the spring; the lighter the weights, the higher the frequency. 
Hooke's Law in IR spectroscopy means: 
● stronger bonds absorb at higher frequencies. 
● weaker bonds absorb at lower frequencies. 
● bonds between lighter atoms absorb at higher frequencies. 
● bonds between heavier atoms absorb at lower frequencies. 

 
 
47. What are the criteria for a molecule to absorb in the IR region? 
A  criterion  for  IR  absorption  is  a  net  change  in  dipole  moment  in  a 
molecule  as  it  vibrates  or  rotates.  Using the molecule HBr as an example, the 
charge  distribution  between  hydrogen  and  bromine  is  not  evenly  distributed 
since bromine is more electronegative than hydrogen and has a higher electron 
density. HBr thus has a large dipole moment and is thus polar. 
 
48. Give the selection rule for IR spectroscopy? 
Selection rules for Infrared transitions  
For a particular vibration to be infrared active there must be a change in 
the  dipole  moment  of  the  molecule  during  the  vibration.  In  other  words,  the 
transition dipole moment must not be zero.  
∆ν = ± 1, transition can take place between Adjacent vibrational levels, 0 
to 1, 1 to 2 etc. 
 
49. What is an IR active and Inactive molecule? Give examples. 
Homonuclear  diatomic  molecules  are  inactive  in  the  infrared  spectrum. 
They  do  not  have  a  dipole  moment to start with and during the vibration also 
the dipole moment is zero. e.g.: H​2, O​2, N​2 etc. 
​ ​ ​

Heteronuclear diatomic molecules such as CO, NO are active in IR. 

Symmetrical  polyatomic  molecules  such  as  CO​2,  the  symmetric ​

stretching  vibration  is  infrared  inactive  whereas  the  asymmetric  stretching 

vibration is IR active. 
 
50. What is the spin selection rule in electronic spectra? 
The  wave  function  of  a  single  electron  is  the  product  of  a 
space-dependent  wave  function  and  a ​spin​ wave  function.  Spin  is  directional 
and can be said to have odd ​parity​. It follows that transitions in which the spin 
"direction"  changes  are  forbidden.  In  formal  terms,  only  states  with  the  same 
total ​spin quantum number​ are "spin-allowed". 
 
51. Write a note on Laporte or orbital selection rule. 
The ​Laporte rule​ is a selection rule formally stated as follows:  
In  a ​centrosymmetric​ environment,  transitions  between  like ​atomic 
orbitals​ such as ​s​-​s​, ​p​-​p​, ​d​-​d​, or ​f​-​f,​ transitions are forbidden. The Laporte rule 
(law)  applies  to ​electric  dipole  transitions​,  so  the  operator  has ​u​ symmetry 
(meaning ​ungerade​,  odd). ​p​ orbitals  also  have ​u​ symmetry, so the symmetry of 
the  transition  moment  function  is  given  by  the ​triple  product​ ​u​×​u​×​u​,  which 
has ​u​ symmetry.  The  transitions  are  therefore  forbidden.  Likewise, ​d​ orbitals 
have ​g​ symmetry  (meaning ​gerade​,  even),  so  the  triple  product ​g​×​u​×​g​ also 
has ​u​ symmetry and the transition is forbidden. 
 
52. Explain the criteria for a molecule to absorb radio frequency waves in the 
NMR region. 
The  NMR  spectroscopy  depends  upon  the  fact  that  most isotopes of the 
elements  possess  gyromagnetic  properties,  which means that they behave like 
tiny  spinning  bar  magnets.  When  a  sample  containing  nuclei  exhibiting  this 
immutable  gyro  magnetism  is  placed  in an appropriate DC magnetic field and 
is  simultaneously  irradiated  by  a  weaker  rotating  radiofrequency  magnetic 
field,  the  nuclei  can  be compelled to reveal their presence, identify themselves 
and describe the nature of their surroundings. 
 
53. What is NMR active and inactive nuclei? Give examples. 
The spin of atomic nuclei can be predicted based on the knowing the 
number of protons and neutrons in the nucleus: 
● Even/Even. Nuclei that contain an even number of protons ​and​ an 
even number of neutrons have I=0 and are NMR silent.  
● Examples: C12 ​ , O16
​
​  and S32
​
​ .  ​

All other nuclei are NMR active​: 

● Odd/Odd. Nuclei that contain an odd number of protons ​and ​ an odd 
number of neutrons have I that are positive integers. Examples: 
H2​  (I=1), N14​ (I=1) and B10​  (I=3). 
​ ​ ​

● Odd/Even & Even/Odd. All other nuclei (odd/even and even/odd) 

have spins that are half integral.  
Examples: H1​ (I=1/2), B11​  (I=3/2), C13​ (I=1/2), O17​  (I=5/2), F19​  
​ ​ ​ ​

(I=1/2) and P31​ (I=1/2). 
​
 
54. What are the two scales used to calculate chemical shift values? 
There  are  two  chemical-shift  scales, viz., the ​δ​-scale and the ​ζ – scale is 
used in recording NMR signals. They are related by the expression 
δ + ζ = 10
i.e., ζ = 10 - δ 
Chemical  shift ​δ​ is  usually  expressed  in ​parts  per  million​ (ppm) 
by ​frequency​, because it is calculated from 
 
where ​ν​sample is the absolute resonance frequency of the sample and ​νref
​ ​  is 
​

the absolute resonance frequency of a standard reference compound, measured 
in  the  same  applied  magnetic  field ​B​0.  Since  the  numerator  is  usually 
​

expressed in ​hertz​, and the denominator in ​megahertz​, ​δ​ is expressed in ppm. 

 
55. Give any two references (or) standards used in NMR spectroscopy. 
The  detected  frequencies  (in  Hz)  for 1​ H, 13​ C,  and 29​ Si  nuclei  are  usually 
​ ​ ​

referenced  against TMS (​tetramethylsilane​), TSP (​Trimethylsilylpropanoic acid​), 
or ​DSS​, which by the definition above have a chemical shift of zero if chosen as 
the reference. 
 
56. What is the shielding and deshielding effect in NMR spectra? 
The Nucleus feels a weaker magnetic field.  
Shielding  is  a  barrier  made  of  inner-shell electrons and it decreases the 
nucleus’  pull  on  the  outer  electrons. Shielding is defined as “a nucleus whose 
chemical shift has been decreased due to addition of electron density, magnetic 
induction, or other effects.” 
The Nucleus feels a stronger magnetic field. 
Deshielding  is  the  opposite  of  shielding.  When  we  say  that  an  atom  is 
deshielded, we mean that “A nucleus whose chemical shift has been increased 
due to removal of electron density, magnetic induction, or other effects.” 
 
57. What is Larmor (or) precessional frequency? 
The ​Larmor  or  precessional  frequency​ in ​MRI​ refers  to  the  rate  of 
precession of the magnetic moment of the proton around the external magnetic 
field.  The  frequency  of  precession  is  related  to  the  strength  of  the  magnetic 
field, ​B​0. 
​

The ​precessional  frequency​ of  nuclei  of  a  substance  placed  in  a  static 

magnetic field B​0 is calculated from the Larmor Equation: 
​

ω = γB 
where ​ω​ is  the  Larmor  frequency  in  MHz, ​γ​ is  the ​gyromagnetic  ratio​ in 
MHz/tesla and ​B​ is the strength of the static magnetic field in tesla. 
 
58. Define the term chemical shift and give the model of NMR spectrum for 
ethanol molecules. 
The  NMR  spectra  is  displayed  as  a  plot  of  the  applied  radio  frequency 
versus  the  absorption. The applied frequency increases from left to right, thus 
the  left  side  of  the  plot  is  the  low  field,  downfield  or  deshielded  side  and  the 
right  side  of  the  plot  is  the  high  field,  upfield  or  shielded  side  (see  the  figure 
below). The concept of shielding will be explained shortly. 

 
  
The  left-hand  cluster  of  peaks  is  due  to  the  CH​2 group.  It  is  a  quartet 
​

because  of  the  3  hydrogens  on  the  next  door  CH​3 group.  You  can  ignore  the 
​

effect  of  the  -OH  hydrogen. Similarly,  the  -OH  peak  in  the  middle  of  the 
spectrum is a singlet. It hasn't turned into a triplet because of the influence of 
the CH​2 group. 
​

 
59. How many values can the magnetic quantum number have? 
The  magnetic  quantum  number  distinguishes  the ​orbitals​ available 
within  a ​subshell​,  and  is  used  to  calculate  the  azimuthal  component  of  the 
orientation of orbital in space. Electrons in a particular subshell (such as s, p, 
d, or f) are defined by values of ​ℓ​ (0, 1, 2, or 3). The value of ​m​l​ can range from 
-​ℓ​ to +​ℓ​, including zero. Thus, the s, p, d, and f subshells contain 1, 3, 5, and 7 
orbitals  each,  with  values  of ​m​ within  the  ranges  0,  ±1,  ±2,  ±3  respectively. 
Each  of  these  orbitals  can  accommodate  up  to  two  electrons  (with  opposite 
spins), forming the basis of the ​periodic table​. 
 
60.  Write  down  possible  values  m  can  have  for  a  nucleus  with  I=1.  Draw the 
energy level diagram for it. 
For  the  proton  in  a  field of  1  T, νL =  42.576  MHz,  as  the  proton  spin 
orientation  flips  from ​+​1/2 to ​−​1/2.  This  transition  is  in  the  radiofrequency 
region of the electromagnetic spectrum. 
  

 
 
 
Module-3 
61. Why is XPS a more qualitative than quantitative technique?
XPS is a more qualitative technique because the spectral interfaces are minimal
Since XPS peaks for the core electrons tend to be fairly widely separated. XPS
elemental analysis is based on core electron peaks usually straightforward.

62. Give the number of electrons and best suitable pressure required for
XPS measurement.
In XPS analysis the electrons emitted from atoms near the sample surface is 10-100
Angstroms and suitable pressure requires for high vacuum chamber is 10 -6​​ pa,for ultra

high Vacuum chamber is P ​⦟ ​10​-7​ pa

63. What is the principle of XPS?

The working principle of XPS is the ejection of electrons from the surface of a sample in
ultra high vacuum (UHV) condition. When an X ray (with energy hv) ejects out an
electron ( by energy B.E). The ejected electron is called a photoelectron and this effect is
 called photoelectric effect. The element present in the sample can be identified on the
basis of kinetic energy (K.E) and the binding energy ( B.E) of their photo electron. The
intensities of photoelectrons provide information about concentration of elements in a
sample.

64. Give only a schematic diagram for XPS instrumentation.

65. What are the merits and demerits of XPS analysis?

Merits
1) XPS analysis is effective across a range of organic and inorganic materials.
2) XPS is a leading technique for analyzing ​stainless steel passivation.
3) XPS is also effective at identifying surface contaminants.
Demerits
1) Size matters.
2) Challenges with reproducibility.
3) Samples must be compatible with a high vacuum environment.

66. Define the terms: Binding energy and Work function in XPS analysis​.
Electron Binding energy ​is a generic term for the minimum energy needed to remove an .
electron from a particular electron shell for an atom or ion,
E​binding ​=​E​photon ​– ( ​E​kinetic ​+ ​∅)
where ​E​binding is the binding energy (BE) of the electron measured relative to the chemical
potential, ​E​photon is the energy of the X-ray photons being used, ​E​kinetic is the kinetic energy of
the electron as measured by the instrument
∅ ​is the ​Work function ​for the specific surface of the material, which in real measurements
includes a small correction by the instrument's work function because of the contact
potential. The work function-like term can be thought of as an adjustable instrumental
correction factor that accounts for the few eV of kinetic energy given up by the
photoelectron as it gets emitted from the bulk and absorbed by the detector.

67. What are the applications of XPS? [Any two]

i. It is used for the surface analysis of organic and inorganic materials
ii. It is used to study the fiberglass surface
iii. It is an unique approach in probing electronic structures.

68. DefineMiller indices with examples​.

Miller introduced a set of integers (​hkl​) to specify a plane of the crystal. This set of three
numbers (​hkl​) is known as ‘Miller indices’ of a particular plane of a crystal. “The Miller
indices ((​hkl​) of a plane of a crystal are inversely proportional to the plane on the
crystallographic axes”
i. It is customary to describe crystal planes by a set of Miller indices.
ii. Find the intercept on the crystal axes as multiples of the lattice constants a​1​,b​2​,c​3
iii. Take reciprocals of these numbers and
iv. Using an appropriate multiplier, convert the 1/intercept set to the smallest
possible set of whole numbers
v. Represent the above as a set of integers (​hkl​) for a given plane of a crystal.

69. For the intercepts x, y and z with values of 3,1and 2 respectively, find the Miller indices
[Give the steps].
i. Intercepts : 3,1,2
ii. Fractional intercepts: 1/3,1/1,1/2 ( reciprocal)
iii. Miller indices: (263)

70. Compute the MillerIndices for a plane intersecting at x=¼,y=1,andz=1/2.[Give

the steps].
i. Intercepts : 1/4,1,1/2
ii. Fractional intercepts: 4,1,2 ( reciprocal)
iii. Miller indices: (412)

71. Give the expression for Bragg’s law and explain the terms involved in it.
Bragg diffraction occurs when radiation, with a wavelength comparable to atomic spacings, is scattered
in a specular fashion by the atoms of a crystalline system, and undergoes constructive interference. For a
crystalline solid, the waves are scattered from lattice planes separated by the interplanar distance ​d​.
When the scattered waves interfere constructively, they remain in phase since the difference between
the pathlengths of the two waves is equal to an integer multiple of the wavelength. The path difference
between two waves undergo interference is given by 2​d​sin ​θ​, where ​θ ​is the glancing angle
2​d​sin ​θ ​= n ​λ
where ​n ​is a positive integer and ​λ ​is the wavelength of the incident wave. A diffraction pattern is
obtained by measuring the intensity of scattered waves as a function of scattering angle. Very strong
intensities known as Bragg peaks are obtained in the diffraction pattern at the points where the scattering
angles satisfy Bragg condition.
72. What is interplanar spacing in lattices? Give the expression taking an example.
The interplanar spacing or interplanar distance is the perpendicular distance between two
successive planes in a family (hkl).
Interplanar Crystal spacing of cubic crystal families is defined as
𝑎
d​hkl ​=

√ℎ​2​+𝑘​2​+𝑙​2

73. Determine the Miller indices (hkl) of the shaded planes below.

Intercepts: 2, ​∞​, 2
Fractional intercepts: 1/2, 1/​∞​, 1/2
Miller indices: (101)

Intercepts: 1, 2, 3 :
Fractional intercepts: 1/1, 1/2, 1/3
Miller indices: (632)

Intercepts: ​∞​, 1, ​∞
Fractional intercepts: 1/​∞​, 1/1, 1/​∞
Miller indices: (010)s

74. Define Bragg’s law and give a diffraction pattern diagram.

The crystal diffract x- rays because the inter planar spacing in a crystal lattice is of the same order as that
of the wavelength of the x-rays
 75. Define the terms i.Criticaltemperature ii.Criticalvolume iii.Criticalpressure.
i. Critical temperature (T​C​). ​It is define as the temperature above which the gas
cannot be liquefied
ii. Critical volume (Vc) . ​The volume occupied by one mole of gas at critical
temperature and pressure is called the critical volume (Vc).
iii. Critical pressure ( P​C​). ​The minimum pressure required to liquefy the gas at the
critical temperature is called Critical Pressure (Pc)

76. Write a short note on ion-ion interactions.

Ion-ion interactions are an attractive force between ions with opposite charges. They are also
referred to as ionic bonds and are the forces that hold together ionic compounds. Like charges
repel each other and opposite charges attract. These Coulombic forces operate over relatively
long distances in the gas phase.

77. What is Dipole-dipole interaction ? Give an example.

Dipole​-​Dipole interactions ​result when two ​dipolar ​molecules ​interact ​with each other
through space. When this occurs, the partially negative portion of one of the polar
molecules is attracted to the partially positive portion of the second polar molecule.
Examples: NH​3​, SO​2​ HF, HCl

78. What are London forces of interactions? Give examples.

The ​London dispersion force ​is a temporary attractive ​force ​that results when the electrons
in two adjacent atoms occupy positions that make the atoms form temporary dipoles. ​The
unequal distribution of electrons about the nucleus in an atom can induce some dipole in the
atom. When another atom or molecule comes in contact with this induced dipole, it can be
distorted that leads to an electrostatic attraction between either atoms or molecules.For
example, consider London dispersion forces between two chlorine molecules. Here both
chlorine atoms are bonded through a covalent bond which forms by equal sharing of valence
electrons between two chlorine atoms. The force of attraction between two ​chlorine
molecules ​is the London dispersion force here which is due to unequal distribution of
electron density in the molecule.

76. Write a note on ion-dipole interactions.

An ion-dipole interaction is an attractive force that results from the electrostatic
attraction between anions and a neutral molecule that has a dipole.Most commonly
found in solutions. A positive ion (cation) attracts the partially negative end of a
neutral polar molecule.A negative ion (anion) attracts the partially positive end of a
neutral polar molecule.

77. What is the modified form of VanderWaals equation?

Vander waals proposed his famous equation of state for a nonideal gas. He modified
the ideal gas equation by suggesting that the gas molecules were not mass points but
behave like rigid spheres having a certain diameter and that there exist intermolecular
forces of attraction between them . The two correction terms introduced by Vander
waals are

78. Give the Clausius equation for real gases.

 79. What are the postulates of Fajan’s rule for ionic and covalent bonds? Give an
example for the bonds mentioned.
The molecules containing high positive charge on cation, high negative charge on anion, smaller
cation or large anion are covalent in character. The molecules containing low positive charge on
cation, low negative charge on anion, large cation or small anion are ionic in character.
In anhydrous chlorides like NaCl, MgCl​2 and AlCl​3​, the polarizing power of the cations Na​+​,
Mg​2+​, Al​3+ increases in order Na​+​< ​Mg​2+ ​< ​Al​3+, since the positive charges on the cations also

increases in the same order. With the increase of polarization of Cl​- anion by the cation (Na​+​,
Mg​2+​, Al​3+​), the covalent character between the cation and anion of these chlorides also increases
as we move from NaCl to AlCl​3.

82. First ionization energy of Al is lower than that of Mg. Comment on the
statement.
 Reason:-

  Electronic configuration of Al = 1s​2​2s​2​2p​6​3s​2​3p​1

Electronic configuration of Mg = 1s​2​2s​2​2p​6​3s​2

 Al has one unpaired electron in its highest energy orbital (3p), and Mg's highest energy orbital
(3s) has the paired electrons. It is easier to remove electrons from unpaired 3p​1​ than from paired
3s​2​.

 It is energetically favorable for all the electrons in an orbital to be paired, which means that
breaking up this pair would require more energy.

84. How many numbers of geometries are possible in C.N4? Give an example.
Two different geometries are possible.
The ​tetrahedron ​is the most common. e.g tetrahedral Cobalt(II) complexes
while the ​square planar ​is found almost exclusively with metal ions having a d​8​ electronic
configuration. e.g cis-PtCl​2​(NH​3​)​2

85. How many numbers of geometries are possible inC.N6? Give an example.
Three different geometries are possible.
Hexagonal planar Geometry​: Unknown for first row transition metal ions, although the
arrangement of six groups in a plane is found in some higher coordination number
geometries.
Trigonal prism Geometry​: Most trigonal prismatic compounds have three bidentate ligands such
as dithiolates or oxalates and few are known for first row transition metal ions.
Octahedral (Oh): ​The most common geometry found for first row transition metal ions,
including all aqua ions.

86. Define the terms i. Ionization energy, ii. Electron affinity and iii.
Electronegativity
i. Ionization energy​- The amount of ​energy ​required to remove an electron from
an isolated atom or molecule.
ii. Electron affinity- ​The amount of energy released when an electron is added to
a neutral atom to form an anion.
iii. Electronegativity- ​The tendency of an atom in a molecule to attract the shared
pair of electrons towards itself.

87. What is effective nuclear charge and Shielding constant? Give their relationship.
The ​effective nuclear charge ​(often symbolized as Z​eff or Z*) is the net positive
charge ​experienced by an electron in a multi-electron atom. The term “​effective​” is used
because the shielding effect of negatively charged electrons prevents higher orbital
electrons from experiencing the full ​nuclear charge​.

Z​eff​ ​can be calculated by subtracting the magnitude of shielding from the total nuclear
charge and the effective nuclear charge of an atom is given by the equation:

Z​eff​ ​= Z-S
88. Give the formula to calculate Shielding constant[σ]for an electron residing in n
[sorp]subshell and also in“d”subshell.
The value of σ for an electron residing in (n – 1)d orbitals of (n – 1)​th​ shell of an atom or an ion

(a) There will be no contribution to the value of s by the electrons residing in ns orbitals
in ns orbital.
 (b) Each of the remaining electrons present in (n – 1) d orbitals, makes a contribution of 0.35
Each of the electrons present in the (n – 1)s, (n – 1)p orbitals and inner shells [i.e. 1​st​ 2​nd​,
3​rd​,….(n – 2)th shells] makes a contribution of 1.0

σ for a (n – 1)d electron = 0.35 × [No. of the electrons in (n – 1)d orbitals] + 1.0 × [No. of
electrons in (n – 1)s, (n – 1)p orbitals and inner shells]

88. List out elements from the following the most electropositive and electronegative
element and give reasons. Li, Be, B, C, K and Fluorine.
Most electropositive element is K and most electronegative element is F
​ ). On moving from
In the above list except K other elements belong to the same period (2 nd​
left to right the electronegativity increases with increase in the number of outer electrons.
Since F is the having more number of electrons in the outermost orbital, it is the most
electronegative element. (present in the top right hand corner of the periodic table)
K is present in the first group. In groups from top to bottom the electronegativity decreases
because of electron shielding effects. So compared with Li on the same group K is less
electronegative. So the K is the most electro -positive element in the given list.

89. Arrange Br, F, I and Cl in the order of increasing electron affinity and give reasons.
F > Cl > Br > I
On moving down the group the electron affinity decreases. Because of the steady increase in
atomic radius of the elements

90. Give the increasing order for Na, Al, Mg and Si atoms based on effective
nuclear Charge and give reasons​.
Na <Mg <Al < Si
All these elements belong to the 3rd period. We know that as we proceed from left to right in
a period, the electrons are added to the orbital of the same main energy level. The addition of
each electron increases the nuclear charge by one, so from Na to Si nuclear charge increases.

91. Give the increasing order for Na, Al, Mg and Si atoms based on effective nuclear charge
and give reasons.
 The order of increasing effective nuclear charge is Na < Mg < Al < Si because, in a period,
on moving from left to right, the electrons are added to the same principal shell. The added electrons
shield each other poorly from the nucleus therefore the effective nuclear charge increases.

92. What are atomic radii? Give its variation along the period and down the group taking
examples.
The atomic radius is defined as one-half the distance between the nuclei of identical atoms
that are bonded together.
In a period, from left to right, with increase in the atomic number, the atomic radius
decreases due to increase in the nuclear charge which increases the attraction of the nucleus for the
valence electrons.
For example, in the elements of the second period, the covalent radii decrease as we move
from Li to F as shown below.
Li (1.23) >Be(0.90) > B(0.82) > C(0.77) > N(0.75) > O(0.73) > F(0.72)
In a group, on moving from top to bottom, the atomic radius increases as a new energy level
is added at each succeeding element but the number of valence electrons remains the same.
Be (0.90) <Mg (1.36) <Ca (1.74) <Sr (1.91) <Ba (1.98)

93. Arrange the following in the increasing order of atomic radii and give reasons: N, S, P
and O.
The correct order of atomic radii of N, S, P, and O follows the order O < N < S < P. On
going from N to O, the nuclear charge increases. But the additional electron is added in the same
energy level. Hence, due to shielding effect, the effective nuclear charge increases. The attraction of
the nucleus for the valence electrons increases. Hence, the atomic size decreases. The atomic size of
N is larger than that of O. For the same, reason, the atomic size of P is larger than that of S.

94. Give reasons for: on-going from C to N in the second period, the values of electron affinity
decrease instead of increasing.
On moving across the periodic table, the electron affinity increases. But, the period from
Carbon to Nitrogen experiences an adverse reaction.
Reason​:
● The electron affinity decreases because the atomic size increases.
● The nuclear force of attraction decreases
● The attraction for an electron becomes less.
Hence, ongoing from C to N in the second period, the values of electron affinity decrease instead of
increasing.

95. Sr has larger atomic size when compared to Mg. Justify.

In general, the atomic size increases from the top to the bottom in any group as the number
of energy levels increases. The electronic configuration of Mg and Sr is
12​Mg: 1s​2​ 2s​2​ 2p​6​ 3s​2
38​Sr:1s​2​ 2s​2​ 2p​6​ 3s​2​ 3p​6​ 3d​10 ​4s​2 ​4p​6 ​5s​2
Looking at the electron configuration we conclude that:
● Magnesium atoms are smaller than Strontium atoms because Strontium has more electrons
(38e−) which will occupy more energy levels (n=5 for Strontium versus n=3 for
Magnesium). As the energy level increases atomic size increases. Therefore Sr has larger
atomic size when compared to Mg.

96. Ca​2+​has a smaller ionic radius than K+. Give reasons.

Ca​2+ has a smaller ionic radius than K+ because it has more nuclear charge. In a given
period, on moving from left to right, the nuclear charge increases without addition of shell. The
increased nuclear charge attracts the electrons more strongly towards the nucleus. This decreases the
ionic size.
97. Define Polarizability and Polarizing power for an ion.
Polarizability :
● It is the tendency of an anion to undergo polarization. It indicates the easiness with which an
anion undergoes distortion in presence of a cation.
● It is directly proportional to the size as well as the negative charge on the anion.
● The larger anions can undergo distortion very easily than the smaller ones.
● It is also important to note that the anions with greater negative charge also undergo
polarization easily.
Polarizing Power :
● The ability of a cation to polarize the anion is referred to as polarizing power.
● It is directly proportional to the charge density, which in turn is directly related to the
charge on cation, while inversely related to the size of anion.
● The polarizing power increases with increase in the size of cation i.e. smaller cations are
very effective in the polarization of anion.
● However, the polarizing power increases with increase in the charge on cation.
 ● Greater the polarizing power of cation and greater the polarizability of anion, greater is the
polarization and hence greater will be the covalent nature.
98. CuCl is more covalent than NaCl. Why?
According to Fajan Rule, Effective nuclear charge in cation having s​2​, p​6​, d​10 configuration
is greater than s​2​p​6 configuration therefore cation having s​2​,p​6​, d​10 configuration is more covalent.
Hence CuCl (configuration s​2​, p​6​, d​10​) is more covalent than NaCl.

Module-4 
99. Give the differences between hard and soft acids.
Hard acid Soft acid
Small ionic radii, Large ionic radii,
High positive charge, Low positive charge,
Empty orbitals in the valence shell Completely filled atomic orbitals
High energy LUMOs. Low energy LUMOs
H+, Li+, Na+, K+, Be2+, Mg2+, Ca2+, Sr2+, Cu+, Ag+, Au+, Hg+, Cs+, Tl+, Hg2+Pd2+,
Sn2+Al3+, Ga3+, In3+, Cr3+, Co3+, Fe3+, Cd2+, Pt2+
La3+, Si4+, Ti4+, Zr4+, Th4+,

100. What are hard acids and bases? Give examples.

● Hard acids consist of small highly charged cations and molecules in which a high positive
charge can be induced on the central atom.
● Examples of Hard Acids: H​+​, Li​+​, K​+​, Ca​2+​, Al​3+​, Sn​4+​, BF​3​, BCl​3​, CO​2​, RCO​+​, SO​3​,
RMgX, VO​2​+​, AlCl​3
● Hard bases are highly electronegative and of low polarizability.
● Examples of Hard Bases: F​-​, OH​-​, NH​3​, N​2​H​4​, ROH, H​2​O, SO​4​2-​, PO​4​3-
● Hard bases react more readily to form stable compounds and complexes with hard acids.

101. What are soft acids and bases? Give examples.

● Soft acids consist of large low charge cations and molecules with relatively high energy
occupied molecular orbitals. Soft acids are readily polarizable.
● Examples of Soft Acids: Cs​+​, Cu​+​, Au​+​, Pt​2+​, Hg​+​, BH​3​, Br​2​, I​2​, RO​+​, quinones
● Soft bases contain larger, relatively polarizable donor atoms.
● Examples of Soft Bases: H​-​, R​-​, CO, PR​3​, C​6​H​6​, SCN​-
● Soft bases react more readily and form stable compounds and complexes with soft acids.
102. Define the terms i. Entropy ii. Enthalpy and iii. Internal energy.
i. Entropy
● Generally, entropy is defined as a measure of randomness or disorder of a system.
Entropy is an extensive property which means that it scales with the size or extent of a
system.
● It is a thermodynamic state function. It depends on the state of the system and not the
path that is followed.
● It is represented by S but in the standard state, it is represented by S°.
● It’s SI unit is J/Kmol.
● It’s CGS unit is called/Kmol.
ii. Enthalpy
● Enthalpy is the measurement of energy in a thermodynamic system.
● The quantity of enthalpy equals the total content of heat of a system, equivalent to the
system’s internal energy plus the product of volume and pressure.
● When a process begins at constant pressure, the evolved heat either absorbed or released
equals the change in enthalpy.
● Enthalpy change is the sum of internal energy denoted by U and product of volume and
Pressure, denoted by PV, expressed in the following manner.
H=U+PV
iii. Internal Energy
● Internal energy U of a system or a body with well defined boundaries is the total of the
kinetic energy due to the motion of molecules and the potential energy associated with
the vibration motion and electric energy of atoms within molecules.
● Internal energy also includes the energy in all the ​chemical bonds​.
● Internal energy is a state function of a system and is an extensive quantity.
● The SI unit of specific internal energy would be the J/g.
● For a closed system the internal energy is essentially defined by
ΔU = q + W
Where
● U is the change in internal energy of a system during a process
 ● q is the heat
● W is the mechanical work.

103. What is the relation between enthalpy and Internal energy?

The relation between enthalpy and Internal energy:

At a constant pressure, the equation for change in internal energy, ∆U = q + w can be
written as
∆U = q​P​ – p∆V
Where q​P represents the heat absorbed by the system at a constant pressure and – p∆V is
the expansion work done due to the heat absorbed by the system.
We can write the above equation in terms of initial and final states of the system as:
U​F​ – U​I​ = q​P​ –p(V​F​ – V​I​)
Or q​P ​= (U​F ​+ pV​F​) – (U​I ​+ pV​I​)
Enthalpy H can be given by H = U + PV. Substituting it in the above equation, we get:
q​P​ = H​F​ – H​I​ = ∆H
Hence, change in enthalpy ∆H = q​P​, which is the heat absorbed by the system at a constant
pressure.
At constant pressure, we can also write,
∆H = ∆U + p∆V
● In exothermic reactions, heat from the system is lost to the surrounding. For such
reactions, ∆H is negative.
● In ​endothermic reactions​, heat is absorbed by the system from the surroundings. For such
reactions, ∆H is positive.

104. What is entropy? Explain its significance.

Entropy is the measure of the disorder or randomness in a system. Entropy is very
significant in thermodynamics. The significances are mentioned below:
● Entropy is a physical quantity. It is equal to the ratio of heat absorbed or rejected to the
temperature.
● It indicates the direction of heat flow.
 ● It helps in determining the thermodynamic state of an object.
● Like temperature, pressure, volume, internal energy, magnetic behavior it expresses the
state of a body.
● The orderliness of an object decreases with the increase of entropy. Hence spontaneous
processes are accompanied by an increase in entropy as well as an increase in the
disorder of the system.

105. Give only the Nernst and Gibbs-Helmholtz equations.

The Nernst equation for the electrode potential at 25​o​ ​is given by

The Gibbs-Helmholtz equation in terms of Free energy (∆G) and enthalpy (∆H) is given
by

106. Define Chemical corrosion. Give the schematic diagram for depicting the mechanism
of oxidation corrosion.
Chemical corrosion takes place due to the direct chemical action of atmospheric gases
such as oxygen, halogen, hydrogen sulphide, sulfur dioxide, nitrogen or anhydrous Inorganic
liquid with metal surfaces.
When oxygen directly attacks the metal surface at low or high temperature oxidation
corrosion takes place this type of corrosion usually occurs in the absence of moisture.
Schematic diagram for depicting the mechanism of oxidation corrosion:
The following reactions take place during oxidation corrosion:

Mechanism:
● Oxygen attacks the surface of the metal under oxidation and this results in the formation
of metal oxide scale.
● The metal oxide scale formed on the metal surface acts as a barrier and prevents further
oxidation.
● If oxidation has to continue either the metal iron must diffuse outwards through the
metal oxide barrier or the oxide ions must diffuse inwards through the barrier.
● Though both transfers occur the outward diffusion of the metal ion is more rapidly than
the inverse diffusion of oxide ions.
● This may be accounted for by the higher mobility of the smaller size of the metal ions
when compared to oxide ions.
107. Define Electrochemical corrosion. Give a neat sketch for depicting the mechanism of
oxygen absorption and Hydrogen evolution corrosion.
Electrochemical corrosion
This type of corrosion takes place
 * When a conducting liquid is in contact with the metal or
*When two dissimilar metals are either immersed partially or dipped in a solution.
* When a metal is exposed to wearing a concentration of oxygen or electrolyte.
Mechanism of oxygen absorption
If electrolyte is neutral or alkaline aqueous solution, corrosion takes place by absorption
of O​2​.
Example​: Rusting of iron in water containing dissolved oxygen occurs by oxygen
absorption mechanism.
At anodic area iron will dissolve by oxidation. The surface of iron is usually coated with
the thin film of iron oxide. But if this iron oxide film develops some cracks, anodic areas are
created on the surface; while the metal (iron) acts as cathodes.
Here the anodic areas are small surfaces while the rest of the surface of the metal forms
large cathodes.
At anode, Fe →Fe​2+​→2e-
The electrons flow to the cathodic area through and will be accepted by O​2​.
At Cathode Fe​2+​ +2OH→Fe (OH)​2
If enough O​2​ is present, ferrous hydroxide easily oxidized to ferric hydroxide
2Fe (OH) ​2​ + ½ O​2​ +H​2​O→2Fe(OH)​3
Ferric hydroxide rust. This product is called yellow rust, which is nothing but Fe​2​O​3​.H​2​O.
If O​2​ is limited, the corrosion product will be black anhydrous magnetite, Fe​3​O​4​.

Mechanism of Hydrogen evolution:

 Evolution of Hydrogen Electrochemical corrosion with evolution of H​2 occurs in an
acidic environment.
At anode Fe → Fe​2+​ + 2e-
At cathode 2H​+​ + 2e- → H​2
Overall reaction Fe + 2H​+ ​ → Fe
Iron tank which acts as an anode undergoes corrosion as Fe atoms from the tank
pass into the acidic solution as Fe​2+​ ions as shown in reaction above.
Free electrons accumulate at cathode Hydrogen ions present in acidic solution take
up these electrons forming H​2 gas as shown in the reaction above. H​2 gas liberates in the form of
bubbles near the cathode.
Thus, hydrogen evolution type of corrosion is nothing but displacement of H+ from
acidic solution by metal ions.

108. Write a note on free energy for corrosion reaction.

In electrical and electrochemical processes electrical work is defined as the product of
charges moved (Q) times the potential (E) through which it is moved. If this work is done in an
electrochemical cell in which the potential difference between its two half-cells is E,and the
charge is that of one mole of reaction in which n moles of electrons are transferred, then the
electrical work (-w) done by the cell must be nE.
In this relationship, the Faraday constant F is required to obtain coulombs from moles of
electrons. In an electrochemical cell at equilibrium, no current flows and the energy change
occurring in a reaction is expressed in equation:
W= ​ΔG ​= -nFE
Under standard conditions, the standard free energy of the cell reaction ​ΔG​˚ is ​directly related to
standard potential difference across the cell, E​˚​.
ΔG​˚​= -nFE​˚
Electrode potentials can be combined algebraically to give cell potential. For a galvanic cell,
such as in the case of corrosion, reaction of positive cell voltage will be obtained if the difference
is taken according to the equation.
Ecell= Ecathode - Eanode
The free energy change in a galvanic cell, or in a spontaneous cell region, is negative and
the cell voltage is positive.
109. What is solubility product, Ksp and give the expression for the solubility product
constant of common salt.
The solubility product constant, ​Ksp​, is the equilibrium constant for a solid substance
dissolving in an aqueous solution. It represents the level at which a solute dissolves in solution.
The more soluble a substance is, the higher the ​Ksp ​value it has.
Consider, in general, a salt of the type AxBy which dissociates as
AxBy xAy+ + y Bx-

The solubility product of the salt is now given by

Ksp = [A​y+​]​x​ [B​x-​]​y

Thus, the solubility product of a sparingly soluble salt forming a saturated solution in
water given by the product of the concentrations of the ions raised to a power equal to the
number of the ions occurs in the equation representing the dissociation of electrolyte.

110. What is an Electrochemical cell or Galvanic cell? Give its representation.

Electrochemical cell or Galvanic cell is a device in which the free energy of chemical
reaction is converted into electrical energy i.e. electricity is produced from a spontaneous
chemical reaction.
Cell representation:
Daniel cell is an example of a Galvanic cell obtained by coupling Zn half-cell and copper
half-cell through a salt bridge.
Zn | ZnSO​4​ (aq) || CuSO​4​(aq) | Cu
Cell reactions:
The electrode reactions of Daniel Cell are:
At anode: Zn Zn​+2​ + 2e- (oxidation)
At cathode: Cu​+2​ + 2 e- Cu(s) (reduction)
​
Total cell reaction: Zn + Cu​+2 Zn​+2​ + Cu.

111. Define Single electrode potential and standard electrode potential. Write the
mathematical expression for the Nernst equation for Zn(s)/Zn2+ (aq) // Cu2+ (aq) / Cu(s) .
Single electrode potential:
It is the measure of tendency of metallic electrodes to lose or gain electrons, when it is in
contact with a solution of its own salt.
Standard electrode potential:
It is the measure of tendency of metallic electrodes to lose or gain electrons, when it is in
contact with a solution of its own salt of 1molar concentration at 25​˚​c.
Nernst equation for Zn(s)/Zn2+ (aq) // Cu2+ (aq) / Cu(s)
In Daniell cell, the electrode potentials of the half cells are written as:
This is the Nernst equation for the Daniel cell.

112. Define Plane of symmetry with an example.

It is defined as an imaginary plane that bisects a molecule in such a way that one half of
the molecule is the mirror image of the other half. The plane of symmetry (​σ) ​is also called a
mirror plane.
Example: The eclipsed conformation of meso-tartaric acid has a plane of symmetry​.

113. Define Centre of symmetry with an example.

 A centre of symmetry is a point within a molecule such that if a straight line is
drawn from any atom of the molecule to this point and then extended equal distance
beyond the point, another identical atom will be found at the end of the line.

Example: a-truxillic acid has a Centre of symmetry​.

114. Define Alternating axis of symmetry with examples.

An alternating axis of symmetry is an axis such that a rotation of the molecule about axis
by 360°/n followed by reflection in a plane perpendicular to this axis generates a
structure indistinguishable from the original. The order of the two operations may be
reversed without change in the result.
Example: a-truxillic acid has a two-fold alternating of symmetry.
115. Differentiate geometrical with optical isomerism.
Optical isomers and geometrical isomers are two types of stereoisomers. The key
difference between optical and geometrical isomerism is that optical isomers are pairs of
compounds which appear as mirror images of each other, whereas geometrical isomers are pairs
of compounds containing the same substituents attached to a carbon-carbon double bond
differently. Thus, optical isomers are non-superimposable mirror images, whereas geometrical
isomers have a difference in the connectivity of substituents to the double bond.
Moreover, another difference between optical and geometrical isomerism is that optical
isomers have similar physical properties, but geometrical isomers have different physical
properties.

116. Mention the types of isomerism exhibited by each of the following pairs:
i. Maleic acid and Fumaric acid ii.n-Butyl alcohol and Diethyl ether and iii. Diethyl ether
and Methyl propyl ether
(i) Maleic acid and Fumaric acid exhibits Geometrical isomerism– fumaric acid trans
form and maleic acid cis form

Trans form Cis form

(ii) n-Butyl alcohol and Diethyl ether exhibits Functional isomerism –They have the
same molecular formula but they differ in functional groups.
CH3CH2CH2CH2OH C​2​H​5​OC​2​H​5
n-Butyl alcohol Diethyl ether

(iii) Diethyl ether and Methyl propyl ether exhibit Metamerism due to unequal
distribution of carbon atoms on either side of the functional group.
CH​3 CH​
​ 2O
​ CH​2 CH​
​ 3 CH​3​ O CH​2​CH​3
Diethyl ether Methyl propyl ether
117. Differentiate Chirality and Achirality with an example for each.

Example: For chiral molecules-​ golf clubs, scissors, shoes and a corkscrew, our hands,
Lactic acid CH​3​−CH(OH)−COOH.

Example: For achiral molecules​ - two pieces of paper, A baseball bat, a hammer, most
socks, Hexane-3-ol (C​2​H​5​−CH(OH)−C​2​H​5​).

118. What are Enantiomers and Diastereomers? Give examples.

Enantiomers:
● Optical isomers that are mirror images are called enantiomers. Enantiomers are stable
isolable components that are differing from one another in three dimensional spatial
arrangements.
● They have identical properties in all respects except in their interaction with planar
polarized light.
● They have the same melting point density, solubility color and reactivity towards acids
and bases.
Example: Lactic acid.
Diastereomers:
● Stereoisomers that are not mirror images of each other are called diastereomers.
● They have different melting points, boiling points and solubility.
● They will have different chemical reactivity towards most reagents.
​Eg: 3-bromo-2-butanol ​which has two asymmetric carbon atoms shows the four isomers.

● It is known that (A) is the mirror image of (B) and (C) is the mirror image of
(D). Thus the four isomers are two pairs of enantiomers.
● Now Comparing (A) with (C), (A) with (D), (B) with(C), and (B) with (D) they are
neither superimposable non mirror images. They are called diastereomers.

119. Write a note on Newman projection with an example.

● In the Newman projection the molecule is viewed along the bond joining the key carbon
atoms.
● The front carbon atom is represented by a central point from which the remaining
three bonds emerge.
● The rear carbon atom is depicted by a circle with the remaining three bonds
pointing out from it.
 ● The angle between any two of these bonds on each carbon is 120°.

Example, the Newman projections of ethane is shown below:

120. What is Sawhorse projection? Give an example.

● Sawhorse projection shows the spatial relationship between the substituents attached to
two adjacent carbon atoms .
● In this representation, the bond between the two carbon atoms is drawn diagonally
and is slightly elongated.
● The remaining bonds are shown by small lines.
● The molecule is viewed from slightly above and to the right of the C-C bond.
● There is free rotation about the C-C bond and the three groups attached to one carbon
may be rotated clockwise or anticlockwise in relation to the three groups attached to the
other carbon atom.
Example: n-butane (CH​3​CH​2​CH​2​CH​3​)
 ● The confirmation I in which the groups on C2 and C3 are oriented as far away from each
other as possible is known as ​staggered​ conformation
● The confirmation II in which the groups on C2 and C3 are nearest is known as ​eclipsed
conformation.

Module-5 
121. What is Sawhorse projection? Give an example.
A ​Sawhorse Projection​ is a view of a molecule down a particular carbon-carbon
bond, and groups connected to both the front and back carbons are drawn using ​sticks​ at
120 degree angles. ​Sawhorse Projections​ can also be drawn so that the groups on the
front carbon are ​staggered​ (60 degrees apart) or ​eclipsed​ (directly overlapping) with the
groups on the back carbon.

Staggered Conformation of Ethane

121.Based on Pourbaix diagram,define the terms passivity and immunity.

The zone in which Iron is present in the form of Iron Oxide is known as Passive zone.
The oxides act as a protective barrier and prevent further corrosion.
At negative potentials and acidic pH, Iron is in the stable form. It is known as
Immunity.
122.Give a neat sketch on Pourbaix diagram.
123.What is Fischer Projection?
The Fischer Projections allow us to represent 3D molecular structures in a 2D
environment without changing their properties and/or structural integrity. The
Fischer Projection consists of both horizontal and vertical lines, where the
horizontal lines represent the atoms that are pointed toward the viewer while the
vertical line represents atoms that are pointed away from the viewer. The point of
intersection between the horizontal and vertical lines represents the central carbon.

124.Give the steps to determine R/S configuration on a Fischer Projection R Cahn-Ingold

Prelog priority rules to determine R/S configuration on a Fischer Projection.

125.Define the terms i. Racemic mixture and ii. Meso Isomers with suitable examples.
A racemic mixture is an equal (1:1) mixture of dextro and levo isomers known as
enantiomers. It contains non-identical isomers. A racemic mixture contains chiral
compounds.
 A meso compound is a molecule having more than one identical stereocenter and an
identical or superimposable mirror image. It has identical mirror images. They are
considered as achiral compounds.

Meso Tartaric acid

126. What are dextro and laevo rotatory isomers? Give examples.
A ​dextrorotatory​ compound is a compound that rotates the plane of polarized light clockwise as
it approaches the observer. if a compound is dextrorotatory, its mirror image counterpart is
levorotatory​. That is, it rotates the plane of polarized light counterclockwise (to the left).
 127.What is a reducing agent? Give an example with an equation.
A reducing agent is an element that loses electrons. The reducing agent means to lose
electrons; it is said to have been oxidized.
The element which undergoes oxidation (gets oxidized) is called the reducing agent.
For example:
4NH​3​​+5O​2​​→4NO+6H​2​​O
In the given reaction, nitrogen is oxidized to NO by gaining oxygen atom. Thus, NH​3​​
is reducing agent as it undergoes oxidation.

128.What is an oxidising agent? Give an example with an equation.

An oxidizing agent is an element that gains electrons. Since the oxidizing agent means to
gain electrons; it is said to have been reduced.
The element which undergoes reduction (gets reduced) is called an oxidizing agent.
For example: 2Mg+O2​→2MgO
In the given reaction, O2​ is reduced by losing oxygen atoms. Thus, O2​
is an oxidizing agent as it undergoes reduction.

129.What is the reaction of the following with Cyclopropane? i.Halogens. HI iii. Sulphuric
acid and iv. Hydrogen

130.What is a medicinal drug? Give the use of Aspirin and Paracetamol.

 A medicinal drug is a medicine that treats or prevents or alleviates the symptoms of
disease.
Aspirin can be used to relieve pain and inflammation caused by rheumatic and
muscular pain, sprains, backache, ​headache​, sore throat, toothache and period pain.
It can also be used to treat flu-like symptoms and reduce fever in adults. In low
doses, it can be used to thin the blood.​ Aspirin given​ shortly after a heart attack
decreases ​the​ risk of death.

Paracetamol is used for reducing ​fever​ in people of all ages. It is used for the relief
of mild to moderate pain. Paracetamol can relieve pain in mild arthritis, but has no
effect on the underlying inflammation, redness, and swelling of the joint.

131.Write the synthesis of Aspirin and its uses.

Aspirin is prepared when ​salicylic acid​ is reacted with ​an​ excess of acetic anhydride and
a small amount of a strong acid is used as a catalyst.

Aspirin​, also known as ​acetylsalicylic acid​ (ASA), is a medication ​used​ to reduce

pain, fever, or inflammation. Specific inflammatory conditions in which ​aspirin​ is
used​ to treat Kawasaki disease, pericarditis, and rheumatic fever. ​Aspirin given
shortly after a heart attack decreases ​the​ risk of death.

132..Give the synthesis and uses of Paracetamol.

 ​Paracetamol​ is made by reacting 4-aminophenol with acetic anhydride. This reaction forms
an amide bond and ethanoic acid as a by- product. When the reaction is complete the
paracetamol​ is then isolated and purified.

133.Explain the role of the following reagents in oxidation/ reduction

reactions.a)NaBH4b)K2Cr2O7c)KMnO4and d) LiAlH4

134.What are addition reactions? Give an example.

The reaction in which an unsaturated hydrocarbon combines with another substance to
give a single product is called an addition reaction.
Example: Ethene reacts with hydrogen when heated in the presence of nickel catalyst to
form ethane:
CH2​=CH2​+H2​ Heat Ni catalyst ​CH3​−CH3​

135.What are substitution reactions? Give an example

A substitution reaction is a single displacement or substitution of compounds reaction
Eg: CH​3​Cl on reaction with a hydroxyl ion (OH-) will produce CH​3​OH.
 136.What are elimination reactions? Give an example.
Elimination reactions​ are commonly known by the kind of atoms or groups of
atoms leaving the molecule. The removal of a hydrogen atom and a halogen atom,
for ​example​, is known as dehydrohalogenation; when both leaving atoms are
halogens, the ​reaction​ is known as dehalogenation.

137.What is Markovnikov’s rule? Give an example to illustrate it.

Markonikoff's rule: When an unsymmetrical reagent is added to an unsymmetrical alkene, the

negative part of the reagent is attached to the unsaturated C atom having less number of
hydrogen atoms.
Thus, when HBr is added to propene, isopropyl bromide is obtained as a major product.Thus,
bromide ion is added to the middle carbon atom (having less number of H atoms) and proton is
attached to the terminal C atom.

138.Illustrate peroxide effect with an example.

The addition of HBr to unsymmetrical alkenes against the Markownikoff's rule is called peroxide
effect or Anti Markovnikov's rule. According to this effect, the negative part of the unsymmetrical
attacking reagent attached to that carbon atom of the double bond of unsymmetrical alkene
which bears the higher number of hydrogen atoms." This reaction takes place in the presence of
peroxide.
PropeneCH3​−CH=CH2​​ +HBr peroxide ​ n−propyl bromide CH3​−CH2​−CH2​−Br​

139.Compare Nucleophilic with Electrophilic substitution reactions.

Electrophilic substitutions involve displacement of a functional group by an
electrophile (generally a hydrogen atom). Electrophiles are species that are attracted to
electrons.
Nucleophilic substitutions involve attack of a positively charged (or partially positively
charged) atom or group by a nucleophile. Nucleophiles are species that can donate an electron
pair.

140.Give an example for bimolecular elimination[E2] and unimolecular nucleophilic

substitution[SN1]reactions.
In an E2 mechanism which refers to ​bimolecular elimination​ is basically a one-step
mechanism.
Here, the carbon-hydrogen and carbon-halogen bonds mostly break off to form a new double
bond.
● However, in the E2 mechanism, a base is part of the rate-determining step and it has a
huge influence on the mechanism.
● The ​reaction rate is mostly proportional to the concentrations of both the
eliminating agent and the substrate.
● It exhibits ​second-order kinetics​.
The E2 mechanism can generally be represented as below. In the below-mentioned
representation, B stands for base and X stands for the halogen.
SN1 reaction corresponds to unimolecular nucleophilic substitution reaction. The order of
reaction is one. The hydrolysis of tert-butyl bromide with aqueous NaOH solution is an example
of SN1 reaction. The rate of the reaction depends on the concentration of tert butyl bromide but
it is independent of the concentration of NaOH. Hence, the rate determining step only involves
tert-butyl bromide. In SN1 reaction, racemic mixture is obtained.

141. What is a free radical addition reaction? Give an example with an equation.
Free-radical addition​ is an ​addition reaction​ in ​organic chemistry​ which
involves ​free radicals​.[1]​
​ The addition may occur between a radical and a non-radical, or
between two radicals.
Free Radical Addition Of HBr To Alkenes With ROOR (Peroxides)

142.What is Structural isomerism? Give examples

The isomers differing in the atomic arrangement of the molecules without any kind of reference
to the spatial arrangement are known as the structural isomers. The phenomenon of these
structural isomers is called structural isomerism.
Structural isomerism is also called constitutional isomerism as per the IUPAC. It is a kind of
isomerism where the molecules have the same molecular formula with different orders and
bondings, as opposed to that of the stereoisomerism.
1-pentanol 2-pentanol 3-pentanol
 143.What is Coordination isomerism? Give examples.
This type of isomerism arises from the interchange of ligands between cationic and anionic
entities of different metal ions present in a complex.
When both positive and the negative ions of a salt are complex ions and the two isomers differ in
the distribution of ligands in the cation and the anion; it is Coordination isomerism.
Example: [Co(NH​3​)​6​][Cr(CN)​6​] and [Cr(NH​3​)​6​][Co(CN)​6​].

144.What are Hydrate isomers? Give examples

Hydrate isomerism or solvate isomers are a special case of ionisation isomerism in which
compounds differ depending on the number of the solvent molecule directly bonded to the metal
ion.
Examples:
● [Co(H​2​O)​6​]Cl​3
● [Co(H​2​O)4Cl​2​]Cl.2H​2​O
● [Co(H​2​O)5Cl]Cl​2​.H​2​O

145. What are Linkage isomers? Give examples.

Linkage isomers are two or more coordination compounds in which the donor atom of at least
one of the ligands is different. This type of isomerism can only exist when the compound
contains a ligand that can bond to the metal atom in two (or more) different ways.
Linkage isomerism occurs with ambidentate ligands that are capable of coordinating in more
than one way.
Another example of an ambidentate ligand is thiocyanate, SCN − , which can attach to either the
sulfur atom or the nitrogen atom. Such compounds give rise to linkage isomerism. Typical
ligands that give rise to linkage isomers are: thiocyanate, SCN⁻ and isothiocyanate, NCS⁻
selenocyanate, SeCN⁻ and isoselenocyanate, NCSe
 146.How many conformations does n-butane have?

Conformation is a property of atoms in which rotation of groups about a carbon-carbon

single bond takes place. The rotation usually results in different spatial arrangements of
the atoms. Butane has
​anti
1. gauche
2. eclipsed
3. fully eclipsed

147.Which conformation is the most stable one in n-butane?

The ​most stable conformation​ of ​butane​ is the ​one​ in which the two terminal methyl groups
are the farthest removed from each other, i.e. the anti ​conformation​. Somewhat less favorable is
the gauche ​conformation​ in which the methyl groups assume a dihedral angle of 60°.
 148.Draw the least stable conformation for n-butane.

Eclipsed conformation is least stable because two methyl groups are closer to each other and the
dihedral angle is O.

149.Illustrate the difference between gauche and staggered.

● In an anti conformer, the largest groups are 180​0​ from each other.
● In a gauche conformer, the bonds are staggered but the largest groups are 60​0​ from each
other.
Because of different steric interactions, the most stable conformer is the anti conformer. The
second-most stable conformer is the gauche conformer.

********