IR Spectroscopy

1. A) Convert the following wave lengths in terms of their wave numbers in cm1.
i) 12.5μ
ii) 285mm
iii) 125mm
iv) 28.5cm
b) What is meant by Electromagnetic radiations? How do the wavelengths and frequencies of
different types of electromagnetic radiations vary?

2. Arrange the following radiations in order of their increasing wave number:

i) UV, X-rays, visible light, Microwave, Cosmic rays
3. Describe some important characteristics of of Electromagnetic radiations.
4. Write a note on electromagnetic spectrum and the absorption of radiations.
5. i) Convert the following wave lengths in terms of their wave numbers in cm-1.
a) 12.5μ
b) 285mm
6. In which region of the electromagnetic spectrum do the following frequencies lie;
i) 40cm-1 ii) 90MHz iii) 12000cm-1 iv) 70000cm-1
7. What is meant by Electromagnetic radiations? How do the wavelengths and frequencies of
different types of electromagnetic radiations vary?

1. What is the basic principle of IR spectroscopy? Discuss its instrumentation.

The carbonyl stretching frequency of an aldehyde is slightly higher than that of the
corresponding methyl ketone. Explain.
2. Write a note on Fermi Resonance and Coupled vibrations.
3. What are the various solvents, generally used in IR techniques? How the change in polarity
of the solvent affect the position of absorption?
4. What is the basic principle of IR spectroscopy? Discuss its instrumentation.
5. Differentiate between the following on the basis of IR spectroscopy a.) propanal
and propanone b.) p-hydroxy benzoic acid and o-hydroxy benzoic acid c.)
dimethylamine and methylamine d) cis and transcinnamicacid
6. What do you mean by Finger print region?
7. What do you mean by fundamental vibrations and overtones? What are the various
solvents which are generally used in IR techniques? How the change in polarity of the
solvent affect the position of absorption?
8. What happens to O-H str position when 10ml of CCl4 is added to 2ml of ethyl alcohol?
9. Describe the range of the Electromagnetic radiations useful for ultraviolet and Infrared
spectroscopy.
10. What is the range of frequencies for visible light? Express it in wavelengths and also in terms
of wave numbers.
11. What is the moment of inertia of rigid diatomic rotor with bond distance equal to 130pm
and the reduced mass equal to 2x1047Kg?
12. What do you mean by fundamental vibrations and overtone?
13. i) Which of the following molecules do not absorb in IR region, give reason
HCl, CO2, CH4, Cl2, CO, H2
14. Compared to the number of bonds in a molecule, there is generally more number of peaks in
the IR spectrum. Explain.
15. How many fundamental modes of vibrations are possible in CO2, H2O, Benzene,Toluene?
ii) Linear molecules have (3n-5) vibrational degrees of freedom whereas nonlinear molecules
have (3n-6) vibrational degrees of freedom. Explain.
16. Explain the working of Infra red spectrophotometer with diagram.
17. Define IR spectroscopy. Describe the various molecular vibrations in the technique. What
is the major requirement for IR absorption?
18. Which of the following molecules do not absorb in IR region, give reason
HCl, CO2, CH4, Cl2, CO, H2
19. What do you mean by Fundamental vibrations and overtones?
20. IR absorption due to carbonyl stretching occurs at higher frequencies than stretching of C=C
bond. Explain.
21. How will you distinguish between cis and trans cinnamic acid?
Using IR spectroscopy, how can one detect the presence of the following
compounds: i) Di ethyl ether and Acetone ii) o-hydroxy benzoic acid and p-hydroxy
benzoic acid iii) Benzyl amine and N,Ndimethyl acetamide
22. Justify the following statements
(a.) Amine absorbed at higher wavelength as compared to protonated amines.
(b.) H-bonding decreases the wave number of absorption in IR spectroscopic studies
ii) What happens to OH str position when 10 ml of Carbon tetrachloride is added to 2 ml of ethyl
alcohol?
23. Explain the following factors which influence the positions of absorption frequencies from
their normal value in IR spectroscopy:
a) Coupled vibrations
b) H-bonding
24. Write the expected infra red peaks for the following compounds: i) Acetophenone
ii) Benzamide iii) Acetic anhydride iv) Methyl benzoate
25. What is the principle of IR spectroscopy?
26. Which of the following molecules are IR active
a.) CH4 (b) O2 (c) C2H4 (d) SO2 (e) CO2
27. Differentiate between the following on the basis of IR spectroscopy
a.) propanal and propanone
b.) p-hydroxy benzoic acid and o-hydroxy benzoic acid
c.) di-methylamine and methylamine

28. Using IR spectroscopy, how can one detect the presence of the following compounds:
i) Acetone and Propanal
ii) o-hydroxy benzoic acid and p-hydroxy benzoic acid
iii) Benzyl amine and N,Ndimethyl acetamide

UV

1. In a LambertBeer’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?
2. 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.
3. Discuss the various types of electronic transitions and explain the effect of the polarity of
the solvent on each type of transition.
4. Draw a block digram of single beam spectrophotometer and state the sources used for UV-
visible studies.
5. Why Benzene is colourless and fulvene, its isomer is yellow and o-nitro Acetanilide is deep
yellow, but p-nitro acetanilide is light yellow.
6. Discuss the Woodward Fieser rules for calculating absorption maximum in dienes.
7.. A compound having concentration 103g/ltr. resulted absorbance value of 0.20 at λmax
510 nm using 1.0 cm cell calculate its absorptivity and molar absorptivity coefficient.
Molecular weight of the compound is 400.
8. Describe the shift in absorption (n-π*) when a more polar solvent is used.
9. When a UV light is passed through the given solution, the radiant power is reduced to 50%.
Calculate the absorbance.
10. . Explain the working of UltraViolet spectrophotometer with diagram
11. Write five applications of UV-vis spectroscopy
12. 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.
13. 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 ?
14. Explain the working of UltraViolet spectrophotometer with diagram. ii) Write five
applications of UVvis spectroscopy
15. Explain the Beer’s law.
16. Identify the type of UV transition in each of the following compounds:
i) Ethanal ii) Acetic anhydride iii) Pentadiene 1,3
17. 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.
18. Applying Woodward Fieser rules, calculate the values of absorption maxima for the
following compounds:
i) 1,3 cyclohexadiene
ii) 1,3hexadiene
iii) homo-annular conjugated diene and double bond extending conjugation
19. Draw a block diagram of single beam spectrophotometer and state the sources used
for UV-visible and IR spectroscopic studies.
20. 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.
21. The carbonyl stretching frequency of an aldehyde is slightly higher than that of the
corresponding methyl ketone. Explain. ii) What do you mean by fundamental vibrations
and overtone?
.
33. Calculate the concentration in μg /mlof 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.
34. What are absorption laws? How is an Ultraviolet spectrum plotted?

NMR

1. Distinguish CH3CH2CH2CHO and (CH3)2CHCHO by proton NMR spectroscopy.

2. Write five applications of NMR spectroscopy.
3. Which type of nuclei show magnetic properties for the purpose of NMR spectroscopy?
4. How many types of orientation take place when a proton is placed in a magnetic field?
5. Define the term 'chemical shift'. Why TMS is used as a standard in NMR spectroscopy?
6. Give the total number signals obtained in NMR spectra and draw their low
resolution spectra:
6. a) isopropyl chloride b) tertbutylbenzene c) methylacetate d)C6H5CH2CH3 e) (CH3)3CNH2
7. Draw low and high resolution spectra of the following compounds:
i) (CH3)3CNH2 ii) (CH2)2Br iii) CH3CH2CHO
8. Explain the following:
a) Spin-spin coupling
b) Coupling constant
c) Equivalent hydrogens
9. Write five applications of NMR spectroscopy.
10. Calculate number of signals and draw low and high resolution spectra:
i) (CH3)2CO
ii) CH3CH2OH
iii) CH3CH(OH)CH2CH3
iv) CH3OCH3

11. i) The compound ‘X’on mass analysis (70ev) gave a molecular ion peak at m/z, 44. On
elemental analysis, it gave C 54.55%, H 9.09%. The solution of the compound in COCl3 on a
60MHz machine exhibited a downfield signal (quartet), which is one third as intense as the
second signal (doublet). The compound responds to the silver mirror test. Identify the compound
‘X’. Give your reasoning.
12. Write five applications of NMR spectroscopy.
13. Explain the following: a) Chemical shift b) Spin-spin coupling c)Upfield and downfield
signals d) Coupling constant e) Equivalent hydrogens
14. Explain, why butadiene exhibits a higher value of λmax for Π-Π* transitions as compared to
ethylene. A compound with molecular formula C4H10O gave 1H-NMR spectrum consisting
of two groups of lines with relative intensities in the ratio of 3:2. Write the structure of the
compound with reason. ii) How many different types of Hatom environments are
present in methyl alcohol? Also mention the ratio of peak areas due to –CH3 group and –
OH group in NMR spectrum.
15. Distinguish CH3CH2COOH and (CH3)2CHCOOH by proton NMR spectroscopy
Why is TMS internal standard used in place of the determination of magnetic field and
frequency measurements?
16. Calculate number of signals in the following molecules and draw their low and high
resolution spectra:
i) (CH3)2CHO
ii) CH3CH2CH2Cl
iii) CH3CH(OH)CH3
iv) CH3COOCH3
17. a) How many normal vibration modes are possible in the linear molecule ethane C 2H6 and in
the non linear molecule C6H6?
b) The force constant for the band in HF is about 9x105 dynes/cm.
i) Calculate the vibrational absorption peak for HF
ii) Calculate the absorption peak for DF.
(i) Explain the effect of polar solvents on i) n-π*
and π-π*transitions.
ii) On what factors Bathochromic and Hypsochromic shift depend? Explain these shifts with
example.
iii) Define the term chromophore. How will you detect the presence of carbonyl group in
aldehydes and ketones?
18. Write five applications of NMR spectroscopy.
19. Predict the number of signals and their multiplicities for the NMR spectrum of pNitrotoluene,
methyl iodide and t-butyl bromide .
20. What do you mean by fundamental vibrations and overtone?
21. What are the electronic factors which influence the absorption frequencies
from their normal value.
22. Describe the various molecular vibrations in the technique. What is the major
requirement for IR absorption?
23. How will you differentiate i) Chlorobenzene from 1,2dichloroethane
ii) Benzene from acetone by NMR spectra?
24. ) Draw low and high resolution spectra of the
following compounds: i) CH3CH2CH2CH3 ii) (CH3)4C
25. a) Aniline absorbs at 280nm (εmax 8600) but in acidic solution, the main band is seen at
203nm (εmax 7500) which is comparable to benzene. Explain why?
b) What structural features may produce bathochromic or hypsochromic effect in an organic
compound?
26. How many NMR signals would you expect to see from each? Draw their low resolution
spectra also .
i) CH3CH2CHO ii) CH3COCH3 iii) CH2=CHCH2OH iv) CH3CH2OH v) CH3OCH3 vi)
CH3CH2CH2CH2CH2OH
27. The UV spectrum of acetone shows two peaks at
λmax = 280 nm, εmax = 15 λmax = 190 nm, εmax = 100
a) Identify the electronic transition for each,
Which one of these is more intense.
28. What is chemical shift, name the internal standard used in NMR spectroscopy and what are
its advantages.
29. (a) Discuss the spectrometer setup for nuclear magnetic resonance spectroscopy.
30. How many types of orientation takes place when a proton is placed in a magnetic
field? ii) What do you mean by shielding and deshielding of a nucleus?
31. What are the basic principles involved in Nuclear magnetic resonance
32. Draw low resolution and high resolution spectra of the following:
i) CH3CH2CHCl2
ii) CH3CCl2CH3
iii) CH2(CH2)2Cl2
iv) CH3CHClCH2Cl

33. Explain the following:

a) Chemical shift
b) Spinspin
coupling
c) Upfield and downfield signals
d) Coupling constant
e) Equivalent hydrogens

34. Why is TMS internal standard used in place of the determination of magnetic field
and frequency measurements? ii) Distinguish CH3CH2CH2CHO and (CH3)2CHCHO by
proton NMR spectroscopy.