UNIT 2
PART 1 UV VISIBLE SPECTROSCOPY
Short Answer Questions:
1. Give principle of uv visible spectroscopy. What is the requirement of a compound to be uv- visible active?
2. What is range of uv-visible spectroscopy
3. Define Lambert Beers Law.
4. Will the value of absorption change, if the path length of beam of light through the sample is doubled and the
concentration is made half.
5. Give labeled ray diagram of colorimeter.
6. Arrange the following in the increasing order of energy
IR, UV- Visible, Microwave
7. Explain why toluene shows higher λmax value than benzene.
8. Electronic absorption band are generally broad. Explain.
9. How will you distinguish between ethyl benzene and styrene.
Long Answer Questions:
1. Derive Lambert Beer’s law. Define term absorptivity and molar aborptivity. Also give limitations of
Lambert beers Law.
2. Define terms: transmittance and λmax.
3. A Solution of thickness 3 cm transmits 30% incident light. Calculate the concentration of the solution, given
Extinction coefficient Є= 4000dm3 mol-1cm-1. (Ans: 4.35 x 10-5 mol dm-3)
4. The percentage transmittance of an aqueous solution of unknown compound is 20% at 250C and 300 nm for
a 4 x 10-5 M solution in a 2 cm cell. Calculate (i) The Absorbance (Ans: 0.699)
(ii) The molar extinction or absorption coefficient (Ans: 8.7 x 103 M-1 cm-1)
(iii) The percentage transmittance o f a 2 x 10-5 M solution in a 4 cm cell. (Ans: 20%)
5. In an absorption cell, the transmittance of a 0.1 M solution of a substance X is 80% and that of 0.1 M solution
of another substance Y is 60% at a given wavelength. What is the transmittance of a solution of a 0.1M of X
and 0.1M Y? (Ans: 48%).
6. A compound having concentration 10-3 g/l resulted absorbance value 0.20 at λmax 510 nm using 1.0cm cell.
Calculate its absorptivity and molar absorptivity values. Molecular weight of compound is 400.
7. What are possible electronic transitions in uv-visible spectroscopy.
8. What allowed and forbidden transitions in uv-visible spectroscopy.
9. Write a note on following terms.
i. Chromophore ii. Auxochrome
iii. Bathochromic shift or red shift
iv. Hypsochromic shift or blue shift
v. Hyper chromic shift vi. Hypochromic shift
10. Explain the absorption and intensity shift in the UV spectroscopy and support with examples. Illustrate, the
effect of polar and non polar solvent on π→π* transition.
11. Explain why butadiene exhibits a higher value for λmax for π→ π* transition than that of ethylene.
12. Identify chromophoric group in following compound.
i. Metanethiol, ii. Butanone, iii. Toluene iv. cyclopentene
13. Identify the geometric isomer of stillbene from the value 294 and 274 nm
14. Explain for aniline, following trends in λmax :
a. In neutral medium λ max 230 nm b. In Acidic medium λmax 203 nm
15. Acetone absorb at 279 nm in hexane whereas the value of λmax in water 264.5 nm. Explain.
16. Which of the following isomers will show the longest wavelength (higher λmax ) of uv absorption.
i. CH2=CH- CH=CH-CH3 AND CH-CH2=CH-CH2-CH=CH2
ii. CH2=CH-CH=CH-CH2-CH3 AND CH2=CH-CH2-CH=CH-CH3
iii. CH2=CH-CH2 CO – CH2-CH2 CH3 AND CH3-CH= CH CO-CH2-CH2-CH3
iv. CH3CH2CO C6H5 AND C6H5CH2COCH3
v. CH3COCH3 AND CH3CHCOCH3
17. The uv spectrum of acetone show two peaks of λmax = 280nm Єmax = 15 and λmax = 190nm Єmax = 100.
i. Identify electronic transitions for each
ii. Which is more intense
18. List all electronic transition possible for
CH3CHO CH3Cl CH2O
PART 2 IR SPECTROSCOPY
Short Answer Questions:
1. Give principle of IR spectroscopy.
2. What is Hook’s Law.
3. Mention the purpose of IR Spectroscopy.
4. Why IR spectroscopy is often characterized as molecular fingerprint?
5. On what are the factors which influence the position of absorption frequencies from their normal value?
6. Methanol is a good solvent for UV bur not for IR determinations. Why?
7. Methane does not absorb IR energy. Why?
8. What is requirement of a molecule to be IR active?
9. Which of the following will show a vibrational absorption spectrum? N2, CO2, OCS, H2O,H2, CH2=CH2, C6H6.
10. Some of fundamental vibrations are IR active while others are not. Explain.
11. How many normal modes of vibration do you expect from CO2, SO2, CHCl3?
12. Double bond and triple bond in CH2=CH2, and CH≡CH do not absorb IR energy, why?
Long Answer Questions:
13. How force constant and mass of an atom is responsible for alteration in IR spectra.
14. What is fingerprint region? Give its significance.
15. Explain normal modes of vibration with the help of AB2 type of bent molecule.
16. Which vibrational modes of the carbon dioxide molecule CO2 will be IR active? Which will be Raman active?
17. Explain functional group region in IR spectroscopy.
18. Write down the absorption position of common functional groups.
ν (C=O) , ν (C-O), ν (O-H), ν (N-H), ν(≡CH), ν(=CH2), ν(-CH3)
19. An organic compound having molecular formula C7H6O shows absorption peaks at 3010, 2700, 1600, 1580,
1520, 1480 and 1720 cm-1 in its IR spectrum . Suggest its structure.
20. How will you distinguish between following pairs by IR spectroscopy
● i. Ethanol and propanone ii. Phenol and cyclohexanol
● iii. Acetaldehyde and acetone iv . C2H5OH and C2H5OC2H5
● v. O-nitro phenol and p- nitro phenol
● vi. O-hydroxy benzoic acid and p- hydroxy benzoic acid
● vii. Carboxyllic acid and ester
21. How inductive effect and mesomeric effect bring about a change in the position of absorption for a
particular bond, Explain it by taking example of C=O stretching.
22. Write a comment on shift of ν (C=O) in following molecule
HCHO – 1750 cm-1, CH3CHO – 1745 cm-1, CH3COCH3 -1715 cm-1
23. How hydrogen bonding change the position of absorption in IR Spectroscopy?
24. Can you distinguish the type of hydrogen bonding by IR spectroscopy?
25. The C-H Stretching vibration in chloroform occurs at 3000 cm-1. Calculate the C-D str. frequency in deuteron
chloroform. (ans: 2190 cm-1)
26. The C-H frequency of a compound observed at 2910 cm-1. Predict the corresponding C-D stretching
frequency whose hydrogen is replaced by deuterium. (2058 cm-1)
27. Calculate the force constant for Carbon monoxide, if this compound absorbs at 2.143 X105 m-1 and its
reduced mass is 1.139 x 10-26 kg (Ans:1857 N m-1)
28. Determine the structure of the compound C3H6O, which shows the following absorption band in IR spectrum;
i) 2950 cm-1 and 1720 cm-1. The compound gives negative test with tollens reagent.
29. A compound having molecular formula C2H4O2, while studied for its IR analysis, resulted the following peaks
of spectrum: (2900-2950) cm-1, 1710 cm-1, and (3500- 3650) cm-1. The compound also gave effervesces with
Na2CO3. Suggest structure of compound.
30. An organic compound X with molecular formula C3H6O absorbs at 1710 cm-1 strongly, when it is reduced with
hydrogen another Y molecule formed having formula C3H8O, In IR spectra of Y’ absorption at 1710 cm-1 was
missing and a band about 3600cm-1 is appeared. What are X and Y?
31. Two isomer a and b of mole. Formula C3H6O give IR absorption band near 3500cm-1 & 1717 cm-1 respectively.
Assign structural formula for both.
32. Out of following pairs which one is expected to absorb at higher frequency for stretching vibrations.
i. HCHO, CH3CHO, ii. C≡C , C=C iii. O-H, C-C
PART 3 MICROWAVE (ROTATONAL) SPECTROSCOPY
Short Answer Questions:
1. Why heavy molecule have closely spaced rotational energy level?
2. Why microwave spectroscopy could be done in gaseous state only?
3. What do you mean by rigid rotor molecule.
4. Write a note on dipole moment.
5. What is requirement of a molecule to be microwave active?
6. Define selection rule. What is selection rule in microwave/rotational spectroscopy?
7. What is stark effect?
8. What are limitations of microwave spectra.
9. Which of the following molecule can have a pure rotational spectrum? Give reason
i. H2, NO, N2O and CH4, OCS, CO2 and N2
ii. C6H6, CH2=CH2, H2O ,CH3I
L ong Answer Questions:
1. Discuss the mechanism of interaction of microwave radiation with rotating molecule.
2. Derive moment of inertia for a rigid rotor linear molecule
3. Give relationship between rotational energy and consecutive wave number.
4. Derive energy difference when electron jumps from lower energy level to higher energy level. Show they are
quantized.
5. Discuss relative intensities of rotational spectra.
6. Mention Application and limitation of microwave spectroscopy.
C 16
7. Calculate the frequency of the j= 3← 2 transition in the pure rotational spectrum of 12 O. The equilibrium
-1
bond length is 112.81 pm. (Ans: 6B =6 x 1.931 = 11.586 cm ).
8. The spacing between the lines in the microwave spectrum of HBr is 16.94 cm-1. Calculate the bond length of
the molecule. (H= 1, Br = 80) (Ans: 142.3 pm)
9. The internuclear distance of NaCl is 2.36 x 10-10 m. Calculate the reduced mass and moment of inertia of
NaCl. Given atomic masses of Cl = 35x10-3 kg mol-1 and Na =23 x10-3. (ans: 2.303 x1026 kg, 1.283 kg m2).
10. The spacing between the lines in the microwave spectrum of H19F is 41.9 cm-1. Calculate the bond length of
the H19F molecule. (Ans: 0.92 Å)
11. Calculate the value if I and r of CO, B=1.92 cm-1 .(Ans: I= 1.46 x 10-46 kg m2, r=1.13Å)
PART 4 RAMAN SPECTROSCOPY
Short Answer Questions:
1. Briefly explain Raman Spectroscopy.
2. Define stoke’s and Antistoke’s radiation.
3. What do you understand by molecular polarization?
4. What is a criterion for a molecule to be Raman active?
5. Explain in brief the rule of mutual exclusion.
6. Explain intensity of Raman lines.
7. What will be effect of temperature on Raman line.
8. Give selection rule for (i) Vibrational Raman effect (ii) Rotational Raman effect.
Long Answer Questions:
1. What is cause of Raman effect?
2. Give difference between IR spectroscopy and Raman spectroscopy.
3. What technological advances have enable the routine use of Raman spectroscopy.
4. Explain briefly (i) Rotational Raman Spectra of diatomic molecule.
(ii) Vibrational Raman Spectra of diatomic molecule.
5. A sample was excited by the 4358Å line of mercury. A Raman line was observed at 4447Å. Calculate the
Raman shift (in cm-1). (Ans: 459 cm-1, stokes line)
6. Using radiation of wavelength 4 x 103 Å, the first stoke’s line appears at a spacing of 350 cm-1 from the
Rayleigh line. Calculate the frequency of first antistoke’s line in wave number.
7. Which of the following spectroscopy (IR/Raman) would you use to measure the vibrational frequency of the
following bonds:
i. The stretching frequency of N14-N14
ii. The C ≡ C str in ethyne (CH≡CH)
iii. The C=O str in acetone
iv. The Re-Re str in compound (CO)5Re-Re(CO)5
