CHEM F313: Instrumental Methods of Analysis

Lecture 06
UV-Vis Spectrometry (contd.)
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Outline
Example of Woodword Rule
, β unsaturated ketones/aldehydes

Today’s Class
 Benzenoid and Aromatic systems
 Charge Transfer Spectra
 Instrumentation

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Benzenoid and Aromatic systems
• Electronic spectrum of Benzene shows good fine structure in gas phase, but less pronounced
in solvents
• 3-bands: Intense 184 nm (emax 47000) called E1 or l1
202 nm (emax 7000) called E2 or l2
weak 256 nm (emax 200) called B or l3
• Alkyl groups show red shift due to the hyperconjugative effect (most in p- lowest in o-)
units l, nm
Base value for PhCHO 250
Base value for PhCOR 246
These Predictive values Base value for PhCOOH or PhCOOR 230
are more approximate Alkyl, Ring Residue o=3, m=3, p=7
and may vary widely, Hydroxyl –OH, Alkoxyl, -OR o=7, m=7, p=25
MORE than the other O- o=15, m=15, p=80
conjugated systems Chloro, o=0, m=0, p=10
Bromo o=2, m=2, p=15
-NH2 o=13, m=13, p=45
-NHR o=0, m=0, p=73
-NR2 o=20, m=20, p=85
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-NHAc o=20, m=20, p=45
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 Examples

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Charge Transfer Spectra
Example: Iodine in Hexane is violet in color while in benzene is brown
• Formation of CHARGE-TRANSFER complexes between pairs of
molecules
• Production of two new Molecular Orbitals and consequently to
new electronic transfer opportunities
• Involves a DONOR and an ACCEPTOR (similar to Lewis acid-base
pairs)
• Electron–rich HOMO of the donor molecule interacts with
electron-poor LUMO of the acceptor
Charge transfer from electron-rich molecule to electron-deficient
molecule. These are named as Charge-Transfer complexes.

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Charge Transfer Spectra
Charge Transfer Donors
NMe2 NH2 OMe

Charge Transfer Acceptors

I2 AlCl3

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Charge Transfer Spectra
 Filled π orbitals in the donor overlap with depleted orbitals in the
acceptor.
 The lower-energy MO for the complex is occupied in the ground
state and transitions from this MO to new upper MO are responsible
for new absorption band.

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Charge Transfer Spectra
The structure of most charge-transfer complexes are visualized as a face-
to-face association on a 1:1 donor:acceptor basis.
+ δ-
δ
I2
Acceptor
Donor
Donor Acceptor
In benzene-iodine case:
λmax for benzene is 255 nm
λmax for molecular iodine in hexane is 500 nm
The charge transfer complex has an intense band around 300 nm with a
tail in the visible region.
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Charge Transfer Spectra
• EQUALLY applicable to inorganic molecules also.
Typically, d-d transitions for transitions metals occur in UV-Vis
region
LMCT and MLCT complexes show color arising out of charge
transfer
2,2'-bipyridine (bipy), 1,10-
phenanthroline (phen), CO,
CN− and SCN−

F-, O2-, N3-

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UV-Vis Spectrometry
Instrumentation

Refer to R1 (Instrumental Methods of Analysis by Willard,

Merritt, Dean, Settle; 7th Edition)
Chapter 6 – Full

Important hints
UV-Vis Light Source
Wavelength Selection (Dispersive devices - Basics only)
Cells and Sampling Devices
Detectors
Expect objective questions from instrumentation

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UV-Vis Spectrometry
Instrumentation
Main features
• Sample absorbs a portion of incident radiation
• The remainder is transmitted to detector
• It is changed into an electrical signal
• Displayed after amplification on a meter, chart recorder or
some other type of readout device

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UV-Vis Spectrometry
Instrumentation
Instruments for measuring the absorption of U.V. or visible radiation are
made up of the following components
• Sources (UV and visible)
• Wavelength selector (monochromator)
• Sample containers
• Detector
• Signal processor and readout
Sources of UV radiation
• Deuterium source
• The power of the radiation source does not change abruptly over
it's wavelength range
• The electrical excitation of deuterium or hydrogen at low pressure
produces a continuous UV spectrum.
• Both deuterium and hydrogen lamps emit radiation in the range 160
- 375 nm.
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UV-Vis Spectrometry
Instrumentation
• Quartz windows must be used in these lamps, and quartz cuvettes
must be used, because glass absorbs radiation of wavelengths less
than 350 nm.
Sources of visible radiation
• The tungsten filament lamp is commonly employed as a source of
visible light.
• This type of lamp is used in the wavelength range of 350 - 2500 nm.
• The energy emitted by a tungsten filament lamp is proportional to
the fourth power of the operating voltage

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UV-Vis Spectrometry
Instrumentation
Wavelength selector (monochromator)
• All monochromators contain the following component parts;
 An entrance slit
 A collimating lens
 A dispersing device (usually a prism or a grating)
 A focusing lens
 An exit slit

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 UV-Vis Spectrometry
Instrumentation
• Polychromatic radiation (radiation of more than one wavelength) enters
the monochromator through the entrance slit.
• The beam is collimated, and then strikes the dispersing element at an
angle. The beam is split into its component wavelengths by the grating or
prism.
• By moving the dispersing element or the exit slit, radiation of only a
particular wavelength leaves the monochromator through the exit slit.

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UV-Vis Spectrometry
Instrumentation
Cuvettes
• The containers for the sample and reference solution must be
transparent to the radiation
• Quartz or fused silica cuvettes are required in the UV region.
These cells are also transparent in the visible region.
• Silicate glasses can be used for the manufacture of cuvettes for
use between 350 and 2000 nm.

Detectors
• The photomultiplier tube is a commonly used detector in UV-Vis
spectroscopy.
• It consists of a photoemissive cathode (a cathode which emits
electrons when struck by photons of radiation),
several dynodes (which emit several electrons for each electron
striking them) and an anode.
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Conclusions

Benzenoid and Aromatic systems

Charge Transfer Spectra
Instrumentation

 Next Class
 Dissociation & Re-emission of Energy
 Infra-Red (IR) Spectrometry

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