Department of Chemistry and Biochemistry
TIET, Patiala
Chemistry (UCB009)
Assignment Solutions (UV- Vis Spectroscopy)
1. Electronic transition: An electronic transition occurs when the valence electrons namely, s, p, and
n electrons, of a molecule are excited from one electronic state to a higher energy electronic state.
Typically, it involves the absorption of UV-Visible radiation. Electronic transitions take place when
absorb UV-visible light (photon energy is associated) and the electrons in a molecule/atom are
excited from lower energy level (E0) to a higher energy level (En), where n=1,2,3….. . The spacing
between energy levels (∆E) in electronic transitions is ~35 to 71 kcal/mole (UV-Vis region).
Vibrational transition: Each electronic state contains several vibrational energy levels. The
transition between vibrational levels having different energy is known as vibrational transition which
requires absorption of an Infra-Red (IR) radiation. Transitions between the lower vibrational energy
level (v0) to higher vibrational energy level (vn) is known as vibrational transitions, where
n=1,2,3….. These transitions require less energy (IR region) than the transitions within electronic
energy levels. The spacing between energy levels are relatively small i.e. 0.01 to 10 kcal/mole.
Rotational transition: Each vibrational state contains several rotational energy levels. The
transition between rotational levels having different energy is known as rotational transition which
requires absorption of a microwave radiation. The spacing between energy levels in rotational
energy levels is even smaller than vibrational energy levels.
Among these, the electronic transition requires a maximum amount of energy whereas
rotational transition requires a minimum amount of energy.
∆ERotational < ∆E Vibrational < ∆EElectronic
2. Atomic spectrum is a line spectrum whereas molecular spectrum is a band spectrum.
Atoms don’t possess any vibrational or rotational energy levels due to absence of vibrational and
rotational motions. So, they undergo only electronic transitions. Hence, a line spectrum is produced.
On the other hand, molecules possess both vibrational and rotational energy levels in addition to
electronic levels as these can vibrate and rotate as well. For any electronic excitation, various
vibrational and rotational energy levels are available and molecule can assume any one of these levels.
On the average, various molecules occupy various different vibrational and rotational excited states
and these levels are closely spaced. Hence, the various lines obtained in the molecular spectrum
are so close to each other that it appears as a band. (Figure shows various possible transition in
molecule leading to band spectrum)
3. The UV radiation region extends from 10 nm to 400 nm and the visible radiation region extends from
400 nm to 800 nm. Near UV Region: 200 nm to 400 nm. Far UV Region: below 200 nm.
4. Absorption of UV radiation causes electronic transitions in a molecule whereas absorption of infrared
radiation results in vibrational transitions in a molecule.
5.
6. Chromophore: Chromophore may be defined as the functional groups containing multiple bonds
capable of absorbing radiations above 200 nm due to n → π* & π → π* transitions. e.g. -NO2, N=O,
C=O, C=N, C≡N, C=C, C=S, etc
Auxochrome: It is a substituent or a functional group, which by itself does not absorb in the UV
visible region but upon attachment on a chromophore, increases the wavelength of absorption (λmax)
and also alters the intensity of absorption. e.g. -OH, -Br, -OR, -NH2, -NHR, -NR2, -SH etc.
Bathochromic shift: When the wavelength of maximum absorption shifts towards a longer
wavelength or towards the red end of a spectrum, it is known as red-shift or bathochromic shift.
Hypsochromic Shift: When the wavelength of maximum absorption shifts towards a shorter
wavelength or towards the blue end of a spectrum, it is known as blue-shift or hypsochromic shift.
Hyperchromic shift: It is defined as an increase in the intensity of absorption.
Hypochromic shift: It is defined as a decrease in the intensity of absorption.
7. (a) Methanol: Possible transition: *, n *
(b) Benzoic acid: Possible transition: *, n *, n *, *
(c) Pyridine: Possible transition: *, n *, n *, *
(d) Ethane: Possible transition: *
8. (i) (a) C6H6 (b) CH2=CH2-CH2-CH2=CH2 (c) C6H5CHO (d) C6H5CH=CH-CH=CH2
λmax is the wavelength at which absorbance (absorption) for the molecule is maximum. Following
is the order:
(i) CH2=CH2-CH2-CH2=CH2 < C6H6 < C6H5CHO < C6H5CH=CH-CH=CH2
(ii) b>a
9. More the no. of double bonds in conjugation, lesser energy is required for π-π* transitions as HOMO
and LUMO gap decreases. This leads to increase in the magnitude of λmax. Compounds having 8
or more than 8 double bonds in conjugation will appear coloured to human eye.
(a) The added conjugation in naphthalene, anthracene and tetracene causes bathochromic shifts of
the absorption bands. So more than >8 double bond will shift the absorption in visible region.
Naphthalene and anthracene absorb radiation in the UV region so they are colorless, while
tetracene absorb in the visible region so it is orange.
(b) Carotene has 11 conjugated double bond, so it will absorb radiation in visible region that’s why
color is orange.
10. Aniline shows blue shift in acidic medium, as the lone pair of electrons on nitrogen is no longer
in conjugation due to protonation.
λmax = 280 nm λmax = 265 nm
(ii) In alkaline medium, p-nitrophenol shows red shift. Because lone pairs on negatively charged oxygen
(phenolate ion) delocalizes more effectively than the unshared pair of electron in parent p-nitrophenol
molecule.
11. The energy gap between σ – σ* is high and comes below 200 nm wavelength. The general UV-Vis
spectrophotometer provides radiations from 200 nm to 800 nm only not below 200 nm. That’s why
this transition from σ to σ* is not observed (even though it is allowed) by general UV-Vis
spectrophotometer.
12. Phenolphthalein and methyl orange are a class of acid-base indicators whereby the chemical
structures and conjugation changes depending on the H+ concentration. Here are the structural
changes:
