UV-vis Spectroscopy

1. Discuss the various types of electronic transitions and explain the effect of the polarity of the solvent on
each type of transition.
2. Explain the various applications of UV-vis spectroscopy, IR spectroscopy and microwave spectroscopy.
3. Why Benzene is colourless and fulvene, its isomer is yellow and o-nitro acetanilide id deep yellow but
p-nitro acetanilide is light yellow.
4. Calculate the concentration in µg ml-1 of a solution of organic compound (mol mass 211.2) in 0.11 M
HCl giving an absorption at its wavelength maxima at 281nm of 0.612 in 4 cm cell. The molar absorptivity
at 281nm is 5372.
6. Predict the transition involved in the following compounds:
i) Alkenes ii) Alkynes iii) Carbonyl compound iv) Azogroup v) Cyanides

7. What is the basic principle underlying UV?

8. Aniline absorbs at 280nm (£max 8600) but in acidic solution, the main absorption band is seen at 203nm
(£max 7500) which is comparable to the benzene. Explain.
9. How will you distinguish between cis and trans 1,3,5-hexatriene.
10. Following four ketones are filled in four bottles and their labels are removed. Measurement of UV
spectra of the contents of four bottles give λmax 221, 249,237 and 258nm. Assign structure to the
appropriate λmax.
11. Calculate λmax for the following compounds (using Woodward –Fieser Rules):
(i) (ii) (iii)
12. Convert the following wave lengths in terms of their wave numbers in cm-1.
i) 12.5μ
ii) 285mm
iii) 125mm
iv) 28.5cm
13. Arrange the following radiations in order of their increasing wave number:
i) UV, Xrays,
visible light, Microwave, Cosmic rays
14. In a Lambert-Beer’s law cell, the aqueous solution of a substance of known concentration
absorbs 10% of the incident radiation what fraction of the incident light will be absorbed by the
same solution in a cell five times as long?
15. Identify the unknown compound having molecular ion peak at 86 having R.I.= 10 whereas base peak at
m/e = 43. The UV spectrum of this compound is determined in 95% ethanol : λ max 280 nm (log ε=1.3).
Prominent IR absorption at 1717cm-1. Proton NMR shows triplet at 0.9, sextet at 1.6, singlet at 2.1 and
triplet at 2.4 ppm.. Identify using rule of thirteen and spectroscopic data. Also mention its IUPAC name.
16. Draw a block diagram of single beam spectrophotometer and state the sources used for UV-visible
studies and explain the working also.
17.. A compound having concentration 103g/ltr. resulted absorbance value of 0.20 at λ
max
510 nm using 1.0 cm cell calculate its absorptivity and molar absorptivity coefficient.
Molecular weight of the compound is 400.
18. Describe the shift in absorption (n-π*) when a more polar solvent is used.
24. When a UV light is passed through the given solution, the radiant power is reduced to 50%.
Calculate the absorbance.
19. Write five applications of UV-vis spectroscopy
20. A monochromatic radiation is incident on a solution of 0.05 molar concentration of an
absorbing substance .The intensity of radiation is reduced to one fourth of the initial value after
passing through 10cm length of the solution .Calculate the value of molar extinction coefficient
of the absorbing substance.
21. Define the following terms:
(a) (i) Bathochromic shift (ii) Hypsochromic shift (iii) Hypochromic and
(iv) Hyperchromic shift
( b) On what factors ( i) and (ii) depend ?
22. Explain the working of UltraViolet spectrophotometer with diagram. ii) Write five applications of
UVvis spectroscopy
23. Identify the type of UV transition in each of the following compounds:
i) Ethanal ii) Acetic anhydride iii) Pentadiene 1,3
32. A solution of thickness 3cm transmits 30% incident light. Calculate the
concentration of the solution, given extinction coefficient= 4,000 dm3 mol-1
cm-1.
24. Applying Woodward Fieser rules, calculate the values of absorption maxima for the
following compounds:
i) 1,3 cyclohexadiene
ii) 1,3hexadiene
iii) homoannular conjugated diene and double bond extending conjugation
25. A solution shows a transmittance of 25 % when taken in a cell of 1.5cm thickness
calculate its concentration if the molar absorption coefficient is 12000 dm3/mol/cm.
26. What are absorption laws? How is an Ultraviolet spectrum plotted? Write the limitations also.
27. Using radiation of wavelength 4x103 Å, the first stroke's line appears at a spacing of 350cm-1 from the
Rayleigh line. Calculate the frequency of the first antistoke's line in wave number.
28. Calculate the energy associated with a radiation having wave length 4000 Å. Give answer in Kcal/mole
and also in Kjoule/mole.
29. Why absorptions of UV and visible radiations can be studied together, but IR absorption studies
are made separately?