1. In the far infrared spectrum of 23Na35Cl an intense line is observed at 378.0 cm-1.

Calculate
(i) force constant (in Nm-1), (ii) zero-point energy (in Joules), (iii) separation between second
and third vibrational levels and (iv) period of vibration of 23Na35Cl.
Ans. (i) k = 117.062 Nm-1
(ii) 3.76 x 10-21 J
(iii) 7.52 x 10-21 J
(iv) 8.82 x 10 –14 s

2. (i)What is the gross and specific selection rule for a molecule to be IR active? (ii) On this
basis would you say Carbon dioxide is IR active or inactive? Justify with appropriate
reasoning. (iii)How many vibrational degrees of freedom are there in this molecule?

3. (i) The molar absorption coefficient (extinction coefficient) for a metal oxalate complex is
40 lit mol-1cm-1 at 650 mμ. Calculate the % transmittance for a 5 cm cell filled with 0.01 M
solution. (ii) “Absorbance is directly proportional to wavelength maximum.” True or False?
Ans. (i) 1%

4. (i) UV visible spectroscopy is most appropriately associated with vibrational transitions.

5. a) Predict the order of carbonyl stretching frequency of the following molecules:

(Hint: Look for the conjugation in the double bond with the C=O group and how force
constant increases/decreases accordingly)

(b) The IR stretching frequencies appeared at approximately 2200 cm-1 for both -C≡C- and -
C≡N stretching. How can these groups be differentiated using IR?

c)
A B

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In the above two compounds you would observe IR peaks at 1674 and 1683 cm-1. Which
functional group is responsible for the above frequencies? Match the frequencies with the
respective compounds with reasoning.

6. a) Which one of the structures given below is best suited for the given IR spectrum?

(A) (B) (C)

b) A compound has the molecular formula C6H12O and its IR spectrum shows a signal that is
a broad peak between 3300 and 3600 cm-1. Select the structure from the following that is
most consistent with the data.

7. The absorbance of copper sulphate solution containing 5 mg Cu/ml was reported as 3.5 at
440 nm. (a) Calculate the molar absorption coefficient, including units, of CuSO4 when a
1.00 cm cuvette/cell was used. (b) What will be the transmittance at the same wavelength if
the solution is diluted to twice its original volume?
Ans. (a) 44.484 Lmol-1cm-1; (b) 0.0178

8. Identify the structure of the compound whose empirical formula is C8H8O and the IR and
NMR spectra are as shown below. Provide the necessary steps/reasoning.

2
9. Identify the structure of the compound with molecular formula C8H10O for which the IR
and 1H-NMR data is as given below.
IR = broad band around 3400 cm-1
1
H-NMR (δ) = 2.2 (s, 3H), 4.6 (s, 2H), 5.3 (s, 1H), 7.08 – 7.13 (m, 4H)

10. Identify the structure of the compound with the molecular formula C5H11BrO2 for which
the 1H-NMR data is as given below. Also, assign the protons to the signals in the final
structure.
1
H-NMR (δ) = 3.38 (s, 3H), 3.52 – 3.54 (m, 4H), 3.59 (t, 2H), 3.82 (t, 2H).

11. What is the frequency shift of the resonance from TMS for a group of protons with δ =
3.16 of an aromatic compound in a spectrometer operating at 900 MHz?
Ans. 2844 Hz.

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12. The frequency separation between protons in a hydrocarbon and TMS is 2181 Hz at
magnetic field strength of 3.52 T in 1H-NMR. Determine the operating frequency of the
instrument.
Ans. 150 MHz.

13. Predict the number of 1H-NMR signals with splitting patterns, for the following
compounds
(a) CH3COCH2CH2CH(Br)CH3

(b)

14. Interpret the given 1H-NMR spectrum for the compound with molecular formula C13H10O
and identify its structure. The compound shows a peak around 1710 cm-1 in IR.

15. Draw the Newman projection structure of 2,3-dichlorobutane when dihedral angles
between two chlorines and two CH3 groups are 180o and 60o, respectively.

16. Draw the most stable and least stable staggered conformations of 1-phenylpropane with
respect to the C1-C2 bond, showing the Newman projections.

17. (i) If the free energy difference between the gauche and anti-conformations of n-butane is
0.9 kcal/mol at room temperature, what would be the percentages of each of these conformers
at equilibrium? (ii) Mention the types of strains present in the following molecules: (a) n-
propane (b) cyclopropane
Ans: (i) Anti = 81%; gauche = 19%

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18. (i) Draw the most stable conformer for (A) 1,2 dichloroethane in the Newman projection
and the most unstable conformer for (B) trans-4-tertbutyl-1-methyl cyclohexane. (ii) Given
that an axial methyl/H interaction is associated with an energy value of 3.8 kJ/mol, prove
which of two conformers of cis-1,3 dimethyl cyclohexane would be more stable (draw the
relevant structures and explain).

19. Draw the most stable chair conformation of (i) trans-1,4-dibromocyclohexane and (ii) cis-
1-tert-butyl-4-methyl cyclohexane.

20. Which of the following molecules have two axial bromines in at least one of their chair
conformations?

21. In the lowest energy conformation of the compound below, how many alkyl substituents
are axial?

22. Draw the two chair conformations of the following molecule and indicate which is more
stable.

23. Are the following molecules chiral or achiral?

24. Draw the possible structures for butadiene as a (i) planar compound and (ii) non-planar
compound.

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25. Comment on the optical activity of the following molecules, by considering their chair
conformation.

26. Assign R/S for the stereo enters in the following molecules.

H OH O CHO
(a) Me
Ph (b) (c) H N
2
CH3
MeHN H

Cl H
H OH CH3CH2
OMe
(b) (c)
(a) (d)
HOH2C CO2H Cl

27. (a) The specific rotation of the R enantiomer of a compound is [α]D20=+760, and its
molecular mass is 151. What is the observed rotation of a 0.75 M solution of this compound
in a 7cm sample path?
Ans: 6.0
(b) (i) Calculate the specific rotation of a chiral compound A, if a solution containing 0.50
g/10 mL of A, is placed in a 5-dm polarimeter tube and its observed rotation at 25 oC (D-
Line) is (+) 1.0o (ii) Find the observed rotation of solution of A, containing 0.35 g/mL in a
5.0 cm tube (D-line).
Ans: (i) + 4o; (ii) (+) 0.7o

28. Which of the following amines could be used (in principle) as a resolving agent for a
racemic carboxylic acid? Give appropriate reasons.

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29. Draw the structures for the optically active and inactive compound with formulae C3I2Br2.

30. Are the following compounds meso (Yes/NO)? Provide explanation.

H H Cl
Br
(i) (ii)
H Br Cl Br

CH2CH3 H

31. Draw all the possible stereoisomers for the compound pent-3-en-2-ol.
32. (a) Determine whether the two structures in each of the following pairs represent identical
compounds, constitutional isomers, or stereoisomers (enantiomers or diasteromers).