1 No.

Questions:
What is auxochrome? Give an example
Answer:
Certain groups, while not producing colour themselves, when present
along with chromophores in an organic substances intensity the colour.
Such colour assisting groups are called cs. The auxochromes are acidic
or basic functions of which the more important ones are listed below :
Acidic: -OH , -SO3H , -COOH
Basic: -NH2 , -NHR, -NR2
FOR example: azobenzene has red colour , while p- hydroxyazobenzene
is brilliant red colour

Chromophore

Azo-benzen(red)
 Auxochrome

p-Hydroxyazobenzene

Q::What do you know that highest occupied molecular orbital?

Answer:
HOMO: HOMO means that highest occupied molecular orbital. LUMO:
LUMO means that lowest unoccupied molecular orbital.
In chemistry, HOMO and LUMO are types of molecular orbitals. Each
circle represents an electron in an orbitals.
Questions: How will you differentiate mordant and vat dyes??
Answer:-
mordant dyes vat dyes

( i ) mordant dyes have no natural ( i ) vat dyes are insoluble in water but
affinity on a fibre. It is applies to the their reduced from is soluble in alkaline
fibre with metal Ions, such as Al, Cu, solution and have a greater affinity to the
Na etc fibre
(ii) mordant dyes is widely use in ( ii) vat dyes are afidely used in cotton
wool. and least to wool and silk
(iii) example of mordant days is (iii) example of vat dyes is indigo
Alizarin

Alizarin

Question: Why does uv- spectrum usually gives broad peak?

Answer:
Every molecule has some absorption for UV rays. and at a particular
wavelength of Uv rays there is a maximum absorption those is called as
λmax . This λmax is a characteristic for every molecule .When we scan the
sample using the UV rays, the sample absorbs the UV rays accordingly
and gives a broad all the different wavelengths of the UV rays and gives
an absorption value for easy wavelengths absorbed , along with the
wavelength at which maximum absorption took place i.e λ max . So, we
get an intense peak for the λmax and that peak denotes the λmax of the
sample.

Question:- what are the vibrational degree e freedom for a linear

molecule?
Answer:-
For linear molecules vibration degree of freedom = 3n-5
Where,
n=number of atoms.
3n= total degree of freedom.

Question:: Give the condition that are satisfied by a molecular to be

an IR active?
Answer:
(i) Organic molecules and functional groups must be
transparent in the portion of the electro- magnetic spectrum
i.e UV and visible region.
(ii) the range of wavelength should be (190-880)nm
(iii) the range of energy should be (125-650) kJ/mol
(iv) the molecule should be polar molecule
Question:: which Lamp is used in UV-Spectroscopy ?
Answer: Using a spectrometer, light with a wavelength range of
190bnm to 800 nm is radiant through the cuvette and absorption
spectrum are recorded. The broad bond light sources use for this are
deuterium lamps (UV) and tungsten halogen lamps ( visible ). Mercury
lamps that emit just a line spectrum are also used

Question: What kind of dehydrating agent are used in desiccator?

Answer: Calcium chloride and silica gel dehydrating agent are used in
desiccators in which case , anhydrous Calcium chloride is better then
silica gel.

Question: Write two names one for dependent and the other for the
independent chromophores?
Answer:
Independent chromophores: when a single chromophore is sufficient
to impact colour to the compound.
Example: Azo group (-N=N-), nitroso (-NO) group.
Dependent chromophores:when more then one chromophore I'd
required to produce colour in the chromogen.
Example: (>C=O) group, (>C=C<) group.
 Question no 6
DESICCANTS
A desiccants is a hygroscopic Substance that is used to Introduce or
sustain a state of dryness (desiccation in its vicinity, it is the opposite of
humectant. Commonly encountered pre-packaged desiccants are solids
that absorbs water. Desiccants for specialized purposes may be in
forms other than solids, and may work through other principles. Such a
chemical bonding water molecules. They are commonly encountered in
foods to retain eripness. Industrially, desiccants are widely used to
control the level of water in stems.. The most common desiccant is
silica and otherwise inert, nontoxic, water insoluble solid. Other
common desiccants include activated charcoal, Calcium sulfate, Calcium
chloride,
Desiccants are used to remove water from solvents, typically required
by chemical reactions that do not tolerate water, e.g. the Grignard
reaction.

Hypsochromic Effect (Blue shift)

Shift of an absorption maximum to shorter wavelength is called
hypsochromic shift or blue shift. This may be caused by change of
medium (π—π* transition undergo hypsochromic shift with an increase
in the polarity of solvent) for examples, acetone absorbs at 279 nm in
hexane, in water λmax 264.5 nm. This blue Shift results from hydrogen
bonding which lowers the energy of the π orbital. This can be produced
when an auxochrome is attached to double bonds where π elections
are available (e.g. C=O)

Stretching Vibration

The position of atoms in molecules are not fixed.They are Subject to a

number different vibrations. Vibration fall into the two main catagories:
They are
(I) stretching vibration
(2) Bonding Vibration
Stretching Vibrations is the change in inter atomic distance along bond
axis. Stretching Vibration are two types:
(I) Symmetric
(II) Asymmetric
0 0
O

symmetric

0 0
O
Asymmetric
Stream Distillation
Steam distillation is a special types distillation for temperature sensitive
materials like nature aromatic compounds. It was a popular laboratory
method for purification of Organic compound. Many organic
compounds tend to decompose at high sustained temperature. Water
or Steam is introduced into the dissolution apparatus. The water
vapour carries Small amounts of the vaporized compounds to the
condensation flask where the Condensed liquid phase separates,
allowing easy collection. This process effectively enables distillation at
lower temperature. When a mixture of two practically immiscible
liquids is heated while being agitated to exposed the surface of each
liquid to the vapour phase, each continent independently exerts its own
vapour pressure as a function of temperature as if the other
constituent were not present. In this way, many organic compounds
insoluble in water can be purified at a temperature well below the
point at which decomposition occurs.

Beer-Lambert Law
Introduction
The Beer-Lambert law (or Beer's law) is the linear relationship between
absorbance and concentration of an absorbing species. The general
Beer-Lambert law is usually written as:
A = aλ * b * c
where ,
A is the measured absorbance,
aλ is a wavelength-dependent absorptivity coefficient,
b is the path length,
and c is the analyte concentration.
When working in concentration units of molarity, the Beer-Lambert law
is written as:
A=ε*b*c
Where, ε is the wavelength-dependent molar absorptivity coefficient
with units of M -1 cm -1 .

Experimental measurements are usually made in terms of

transmittance (T), which is defined as:
T=I/Io
where ,I is the light intensity after it passes through the sample and I o
is the initial light intensity. The relation between A and T is:
A = -log T = - log (I / I o ).
Absorption of light by a sample Modern absorption instruments can
usually display the data as either transmittance, %-transmittance, or
absorbance. An unknown concentration of an analyte can be
determined by measuring the amount of light that a sample absorbs
and applying Beer's law. If the absorptivity coefficient is not known, the
unknown concentration can be determined using a working curve of
absorbance versus concentration derived from standards.

Limitations of the Beer-Lambert law:

The linearity of the Beer-Lambert law is limited by chemical and
instrumental factors. Causes of nonlinearity include : deviations in
absorptivity coefficients at high concentrations (>0.01M) due to
electrostatic interactions between molecules in close proximity
scattering of light due to particulates in the sample fluorescence or
phosphorescence of the sample changes in refractive index at high
analyte concentration shifts in chemical equilibria as a function of
concentration non-monochromatic radiation, deviations can be
minimized by using a relatively flat part of the absorption spectrum
such as the maximum of an absorption band stray light

Fluorescence
Emission of electromagnetic radiation, usually visible light, caused by
excitation of atoms in a material, which then reemit almost
immediately (within about 10−8 seconds). The initial excitation is
usually caused by absorption of energy from incident radiation or
particles, such as X-rays or electrons. Because reemission occurs so
quickly, the fluorescence ceases as soon as the exciting source is
removed, unlike phosphorescence, which persists as an afterglow. A
fluorescent light bulb is coated on the inside with a powder and
contains a gas; electricity causes the gas to emit ultraviolet radiation,
which then stimulates the tube coating to emit light. The pixels of a
 television or computer screen fluoresce when electrons from an
electron gun strike them. Fluorescence is often used to analyze
molecules, and the addition of a fluorescing agent with emissions in the
blue region of the spectrum to detergents causes fabrics to appear
whiter in sunlight. X-ray fluorescence is used to analyze minerals.

Question no 3
(a)

Chromophore Auxochrome

The colour of organic compounds is due to Certain groups, while not producing
the presence of certain multiple boned coloured themselves, when Pregnant along
with Chromophore in an Organic Substance
groups called chromophore. And a
intensity the colour. Such colour assisting
molecule containing such groups as groups are called Auxochrome.
It is any group which does not Self act as a
chromogen.
Chromophore but whose Presence brings
Or it is defined as any isolated covalently about a shift of the absorption band
towards the red end of the spectrum (longer
boned group that shows a characteristic
wavelength).
absorption in the ultra-violet or the visible The auxochromes are acidic ore basic
functions.
region.
Important auxochromes are:
Important chromophores are:
ACIDIC:-OH , -S03H , -COOH
BACIS: -NH2 -NHR , -NR2

An Auxochrome group is called colours

enhancing group. Auxochrome groups do
not show characteristic absorption above
200 mµ Same common auxochromic groups
are : -OH, -OR,-NH2,-NHR,-NR2,-SH

3B
 Hypsochromic Effect (Blue shift):
It is an effect by which the absorption maximum is shifted towards
longer wavelength due to the presence of an Auxochrome. The π—π*
transition for Carbonyl Compounds experiences bathochromic shift
when the Polarity of the solvent
Decreased

Hypsochromic effects: It is an effect by which the absorption maximum

is shifted towards shorter wavelength (fig: 1)

It may be caused by the removal of conjugation and also by changing

the polarity of the solvent the acidic solution of aniline
 +
NH3

(formed ) is an example of blue shift.

Hyperchromic effects: It is an effect where the intensity of absorption
maximum increases i.e. Emax increase.
For example, the B-band for pyridine at E max 2750 is shifted to Emax 3560
for 2-methyl Pyridine.

HyPohromic effect:
It is an effect where the intensity of absorption maximum decreases i.e.
Emax decreases. For example, Biphenyl absorbs E max 19000 whereas 2-
methyl biphenyl absorbs Emax 10250

Questions 3c: What is dye? Write down the criteria of dye?

Answer:
Dye can generally be described as a colour substance that has an
affinity to the substance to which it is being applied. Dye is class of
colored compound that can Firmly fixed to the fabrics by physical and
chemical bonding.
All colored compounds are not dyes.to be useful as a dye a compound
must show fastness to light, washing, heat and bleaching.

Criteria of a dye:
1. It must have a suitable color.
2. It he able to fix itself on be capable of being fixed to fabric.
3. The fixed dyes must have fastness properties
 fastness to light , heat, bleaching
 resistance to the action of water , dilute acids , alkaline, various
organic solvent used in dye cleaning

Questions 3d: Azo-dyes

The Azo-dyes represent the largest and most important Group of dyes.
Azo dyes are dyes with -N=N-, Structure as a chromophore.
Azo are the compounds containing the functional groups(R-N=R') in
which R and R' can be either
Alkyl or aryl. The -N=N- group is called Azo group.
1. As a consequence of π delocalisation aryl azo Compounds have with
colour especially reds orange and yellow. Therefore they are used as
dyes and are commonly known as azo dyes. All akyl Azo compounds are
usually stable, crystalline species.
2. An example of which is disperse orange-1 same Azo compounds. E.g.
methyl orange are used as acid base indicators due to the efficient
colours of their acid and salt forms the development of Azo dyes was an
important step in the development of the chemical industry
Conversion of primary aromatic amines into diazonium compounds by
treatment with sodium nitrate in excess hydrochloric acid.
NaNO2 +HCl HNO2 +NaCl

Step 2:-
Coupling of diazonium compound with phenol napthols or other
aromatic amines. Coupling with phenols & napthols is carried out in
basic solution.
OH
N2+ Cl- + OH
-HCl N=N

The above reaction carried out al low temperature (0-5)°C becomes

diazonium compounds are usually in the resulting dyes an aromatic
system joined to the Azo group is chromophore and the hydroxy group
or amino group in auxochrome.
Answer 5:

Molecular orbital diagram for alkane:

H
H
H C C H
H H

SP3 Hybridization

3 3
SP SP
E

Electronic transition: σ to σ*
Molecular orbital diagram for alkene:

Electronic transition: π—π*

Molecular orbital diagram for carbonyl compound:

..
C=C: Here both C and O2 are sp2 hybridized
 0

non bonding
O

Electronic transition: n—π*

5B ANSWER
A selection rule describe how the probability of transitioning from one
level to another cannot be zero. It has two sub-pieces. A gross selection
rule illustrates characteristic requirements for atoms on molecules to
display a Spectroscopy or a microwave spectroscopy.
Once the atom of 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 level
due to absorption or emission of electromagnetic radiation. Incident
electromagnetic radiation presents an oscillating with a transition
dipole.
The dipole operator is where "r" is a vector pointing in a direction of
space. A dipole moment of given state is

µz = ∫ ψ *µz ψ dT………………..(1)

A transition dipole moment is a transient dipolar polarization created

by an interaction of electromagnetic radiation with a molecule.
(µz )12= ∫ ψ *µz ψ 2 dT……………..(2)

In an experiment we present an electric field along the z axis (In the

laboratory frame) and we may consider specifically the interaction
between the transition dipole along the X, Y or Z axis of the molecule
with the radiation. If µz is zero then a statement of when µz is non-zero.
We can consider selection rules for electronic rotational and vibrational
transitions.

Uv-visilbe choice of solvent:

The solvent should completely solubilize the Sample at the desired
concentration. The solvent should be UV transparent at the measuring
a wavelength so as not to cause interference which could affect
quantitative result. Table-1 with some common solvent along with their
UV cut of (below this wave length they should not be used for
quantitative determinations) when using volatile solvents stopped cells
should be employed to eliminate evaporation which can lead to
changes in solution concentration and ultimately affect quantitation.