Sachi SPECTROSCOPY NOTES PDF
Sachi SPECTROSCOPY NOTES PDF
Sachi SPECTROSCOPY NOTES PDF
Significance of Spectroscopy:
• Less time consuming.
• Very small amount of sample required.
• Substance remains unchanged during spectroscopic examination and can be used again for other
tests.
• Cost effective
Electromagnetic radiation consist of discrete packages of energy which are called as photons.
A photon consists of an oscillating electric field
(E) & an oscillating magnetic field (M) which are
perpendicular to each other.
Frequency (ν):
– It is defined as the number of
times electrical field radiation
oscillates in one second.
– The unit for frequency is Hertz
(Hz).
1 Hz = 1 cycle per second
Wavelength (λ):
– It is the distance between two nearest parts of the wave in the same phase i.e. distance
between two nearest crest or troughs.
Wavenumber ( ʋ ):
– It is ,the number of wave cycles per centimeter
, which is the reciprocal of wavelength and is
-1
expressed in cm .
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
Depending upon the EMR absorbed or emitted by an atom or molecule, any of the following two types of
spectrum can be used in a particular type of spectroscopy:
(i) Absorption Spectrum: It results when an atom or molecule undergoes a transition from the lower
energy level to the higher energy level with the absorption of a photon of energy hν, provided hν is exactly
equal to the energy difference ( ∆E = E2 – E1 ) between the two levels.
(ii) Emission Spectrum: It results when the atom or molecule falls from the excited state to the ground
state with the emission of a photon of energy hν.
Depending upon the type of species (atom/ molecule etc.) involved, spectra can be divided as:
(i) Atomic Spectrum: It arises from the transitions of an electron between the atomic energy levels.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
(ii) Molecular Spectrum: It arises from the transitions of an electron between the molecular energy levels.
Molecular spectrum gives more information about the structure as it not only includes electronic energy
(atomic spectrum) but also vibrational energy, rotational energy and translational energy.
( Etranslational The translational energy is very small , it is dissipated as heat and not involved in the
molecular spectroscopy.)
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
Q.1 What is Absorbance Law or Beer-Lambert’s Law. Derive and write its limitations.
Ans. The Beer-Lambert ‘s Law :It states that for a parallel beam of monochromatic radiation passing
through a homogenous solution the absorbance is proportional to the product of the concentration and path
length.
A ∝ c. l
A = c. l
where:
A = absorbance
ε = absorptivity
l = pathlength
c = concentration
ε is absorptivity constant. Its value depends on the substance, solvent, wavelength and the units used for the
concentration and path-length
Derivation:
When a beam of monochromatic light is passed through a solution of an absorbing substance, the
rate of decrease of intensity of radiation (‘dI’ ) with thickness of absorbing solution (‘dl’) is directly
proportional to the intensity of incident radiation (I), as well as concentration of the solution( c).
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
When intensity is I0 (incident), the path length is zero and when intensity becomes It (transmitted), the path
length becomes l;
I = Io at l = 0
I = It at l = l
We get,
∫ ∫
where,
ε = K/2.303, is called the absorption coefficient or absorptivity
log Io/ I = A, is called the absorbance
;
𝑨 𝛆𝑪𝒍
Transmittance (T): It is the ratio of the intensity of transmitted light ( I ) by the sample to the intensity of
incident light on the sample ( Io ).
T = I / Io
%T = T x 100
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
(ii) Molar absorptivity (εm ): Molar absorptivity is the absorbance at specific wavelength when the molar
concentration is 1mole/L and the path length is 1cm. m = Lmole -1 cm-1
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
Practice Questions:
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
(ii) Detection of impurities: UV- visible absorption spectroscopy is one of the best methods for
determination of impurities in organic molecules. Additional peaks can be observed due to impurities in
the sample and it can be compared with that of standard raw material.
(iii) Quatitative analysis: Determination of molecular weight using Lambert’s Beer’s law. A=c.l
where: A = absorbance, ε = absorptivity ,l = path length ,c = concentration
(v) Qualitative analysis: UV- visible absorption spectroscopy can be characterize those types of
compounds which absorb UV-visible radiation. Identification is done by comparing the absorption
spectrum with the spectra of known compounds.
(vi) Study of kinetics of chemical reaction . The UV-visible radiation is passed through the reaction
cell and the absorbance changes can be observed. As we know that absorbance is directly proportional
to concentration.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
(vii) Quantitative analysis :Used in quantitative analysis of pharmaceutical substances and drugs.
Ans. Absorption of UV-Visible radiation by an organic molecule leads to electronic transitions between
various energy levels. These transitions consists of an excitation of an electron from an occupied molecular
orbital to unoccupied molecular orbital.
I. σ → σ* transition:
• These transition occur by the saturated hydrocarbons.
• Transition occur by σ electron from bonding orbital is excited to corresponding σ* anti-bonding
orbital.
• These transition require higher energy and thus absorb radiation at lower wavelength.
• e.g. Methane , ethane propane etc.
II.n → σ* transition:
• These transition occur by the saturated compounds containing atoms with lone pair of
electrons like O, N, S and halogens .
• They are capable of n → σ* transition.
• These transitions usually requires less energy than σ → σ* transitions.
• e.g. Amine, aldehydes, alcohol , alkyl halide, ethers, etc.
III. π → π* transition :
• These transition occur by the π electron in a bonding orbital to corresponding anti-bonding orbital
π*.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
• These transition are associated with compounds containing double or triple bond and aromatic
compound.
• These transition require less energy and occur at higher wavelength.
• Compounds like alkenes, alkynes, carbonyl, nitriles, aromatic compounds, etc undergo π
π* transitions.
IV.n → π* transition :
• Unsaturated compounds containing heteroatoms such as O,N,S show this type of
transition.
• An electron from non-bonding orbital is promoted to anti-bonding π* orbital.
• Compounds containing double bond involving hetero atoms (C=O, C≡N, N=O) undergo such
transitions.
• n → π* transitions require minimum energy and show absorption at longer wavelength around
300 nm.
• Aldehydes, ketones, cyanides, carboxylic acid etc.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
(b) Auxochrome
An auxochrome is colour enhancing group.
When it is attached to chromophore, it changes intensity as well as the wavelength
of the absorption maximum.
They are saturated groups having lone pairs of electrons .
Auxochrome generally increases the value of absorption maxima by extending the conjugation
through resonance.
e.g NH2 , OH, OR, NHR, –SH etc.
Note: Benzene is colorless but aniline is yellow in color due to presence of an auxochrome –NH2 in
aniline.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
(iv)Hypochromic shift :-
• The effect which cause the
decrease in the intensity of
absorption maximum (ε max ) is called
hypochromic shift.
• It is caused by the groups
which distorts the geometry of the
molecule.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
When double bonds are conjugated in a compound λmax is shifted to longer wavelength.
e.g. 1,5 - hexadiene has λmax = 178 nm
2,4 - hexadiene has λmax = 227 nm
Solvent effect:
• The most suitable solvent for UV spectroscopy is the one which does not absorb in the region
under investigation .
• Example: Ethanol, Hexane , Methanol , Cyclohexane etc.
• The position & intensity of absorption is affected by the polarity of the solvent.
• Following shifts are absorbed on changing the polarity of the solvents:
Conjugated dienes and aromatic hydrocarbon experienced very little shifts on changing the polarity
of solvents.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
The polar compounds show a change in absorption maximum on changing the polarity of the
solvent .
unsaturated carbonyl compounds (ex: methyl vinyl ketone (butenone) or CH2 =CHCOCH3 )
show two different shifts on increasing the polarity of the solvent.
n → π* transition
• A net increase in energy required for a n → π* transition is thus
observed in protic solvents like water or alcohols.
• Increase in energy will reflect a decrease in wavelength.
• Hydrogen bonding stabilizes n more than * in polar solvents.
• Thus absorption band moves to shorter wavelength i.e. blue shift by
increasing the polarity of the solvent.
π → π* transition
• In the presence of a polar solvent , the more polar π* orbital will be more stabilized then π orbital
leading to a net decrease in the transition energy.
• The dipole –dipole interaction with the solvent molecules lower the energy of excited state more
than that of the ground state.
• Absorption band moves to longer wavelength i.e. red shift by increasing the polarity of the solvent.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
1.RADIATION SOURCE:
• The incident light of required wavelength is provided by different sources for different
spectroscopic technique.
• In ultra violet spectrometers the most commonly used radiation sources are –
hydrogen discharge lamp
deuterium lamp
tungsten lamp
mercury lamps .
• The sources of radiation must meet the following requirements:
a. It should be stable.
b. It should provide continuous radiation.
2. FILTER OR MONOCHROMATOR:
• For conversion of polychromatic radiation from source into monochromatic radiations, the devices
like filters or monochromators are used.
3. SAMPLE CONTAINERS OR SAMPLE CELLS
The sample is placed in the sample container which are cuvettes
Cuvettes:
• Cuvettes are generally made of quartz if work has to be done in ultra violet region.
• Cuvettes may be rectangular or cylindrical in shape .
Test Sample:
• The sample to be analyzed is placed between the detector and monochromator.
• The walls of the cell in which the test sample is placed should be transparent to the radiation used.
4. DECTECTORS:
• Detectors are used to measure accurately the absorption of an analyte via the intensity of the
transmitted light.
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B.Tech First Year 2020-21 Engineering Chemistry (KAS102T/202T)
Short Questions:
Q.a Explain the variation in the value of λmax for the following compound:
CH3 Cl λmax = 173 nm , CH3 Br λmax = 204 nm , CH3 I λmax = 258nm
Ans. All the compound undergo n →π* transition. As we move down the group , the quantum number
increases from Cl to I and hence the n electron lie far away from the nucleus. Thus these are easily excited
and λmax occur at higher value.
Q.b Most of the absorption band in UV-Visible spectra are very broad.Why?
Ans. The electronic transition in UV-Visible may take place with several vibrational and rotational energy
levels.
Practice Questions:
Q.(1) Which one of the following have higher λmax in U.V. spectroscopy.
(i) 1,3 pentadiene and 1,4 pentadiene
(ii) Anthracene and Benzene
(iii) CH3 COCH3 and CH2 =CH- CO- CH3
Q.(2) Identify the type of absorption n →π* , n →σ* & π → π* among the following compound.
a. CH3 COCH3 b. CH3 OH c. CH2 =CH2 d.CH2 =CH-CH=CH2
Q.(3) For a solution of camphor in hexane in a 10cm cell, the absorbance A was found to be 2.52 at
295nm with =14 . What is the conc. of camphor.
Q.(4) Acetone absorb at 279 nm in hexane whereas the values λmax in water is 264.5 nm. Explain.
Q.(5) Explain why polar solvent usually shift π → π* transition to longer wavelength and n → π*
transition to shorter wavelength .
Q.(6) Cis stilbene absorb at 274 nm and trans stilbene absorb at 294 nm. Explain.
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