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.
Given: ϋ = 378.0 cm-1; c = 3 x 1010 cms-1; 1 amu = 1.66 x 10-27 kg
(i) μ = mNax mCl/ (mNa+ mCl) = 23 x 35 x 1.66 x 10-27 kg = 2.304 x 10-26 kg
23 + 35
ϋ = 1/2πc (k / μ) ½ hence k = (2πcϋ) x μ ;
2

On substituting the above values we get k = 117.062 Nm-1

(ii) Zero point energy, E0 = ½ hν; ν = ϋc = 378.0 cm-1 x 3 x 1010 cms-1 = 1.134 x 1013 s-1;
Hence E0 = ½ x 6.62610-34Js x 1.134 x 1013 s-1 = 3.76 x 10-21 J
(iii) Separation between second and third vibrational levels = hν = 2E0 = 2 x 3.76 x 10-21 J =
7.52 x 10-21 J
(iv) Period of vibration, T = (ϋc)-1; Hence T = 8.82 x 10 –14 s
E=1/2hν = ½ x6.625x10-34x 3x108x2144 x1/10-2 m = 21306 x 10-26/10-2 = 2.13x10-20 J

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?

Ans: (i) Gross selection rule is that there should be a change in the dipole moment of a
molecule as a result of vibration. The specific selection rule is Δv=±1. (ii) In CO2 the
symmetric mode is IR inactive, while the asymmetric and bending modes are IR active
(please see lecture slides for depicting the modes). Hence, CO2 is IR active. (iii) Four
vibrational degrees (3N-5) for linear 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?
(i) A= Cl = 40 x 0.01x 5= 2 , A= -log T or, T= 10-2 = 0.01 = 1% (ii) False. Absorbance is
directly proportional to concentration of the complex.
4. (i) UV visible spectroscopy is most appropriately associated with vibrational transitions.
Justify for or against this statement. (ii) Crotonaldehyde, CH3CH=CHCHO has a strong
absorption at 46,950 cm-1 (213 nm) and a weak absorption at 30,000 cm-1 (333 nm). Assign
these absorptions to the precise electronic transitions. (iii) Butadiene shows absorption
maxima at 185 nm and 222 nm. Assign the electronic transition corresponding to these
absorptions in the molecule.

Ans. (i) This statement is not most appropriate as UV Vis spectroscopy involves the
transitions of electrons in the various molecular orbitals of a molecule or compound. Hence,
it is more appropriate to associate UV vis spectroscopy to depict the electronic transitions in a
molecule.

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 (ii) Generally, E (n -*) <E (-*)
In CH3CH=CHCHO, the weak absorption at 30,000 cm-1 (333 nm) corresponds to n -*
of carbonyl group.
The strong absorption at 476,950 cm-1 (213 nm) corresponds to -* transition of the
C=C bond

(iii) 185 nm corresponds to σ → σ* transition 222 nm corresponds to π → π* transition

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

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

(b) The stretching frequencies appeared at approximately 2200 cm-1 for both -C≡C- and -
C≡N stretching. How can these groups be differentiated using IR?
Ans: The intensity will be much higher for –CN than acetylene.

c)
A B
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 and match with the respective
compounds with reasoning.
Ans: The functional group responsible is C=O. Structure B has a methoxy group which is
electron releasing and is more in conjugation with the ring hence C=O will be observed at
lower wave number as compared to structure A.

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

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 (A) (B) (C)

Ans: (B) Ester compound (since you see a strong IR absorption at 1752 and 1055 cm-1
corresponding to C=O and C-O respectively)

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 that is most consistent.

Ans: Cyclohexanol (OH group shows broad signal due to hydrogen bonding)

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.
C = 5 mg/ml = 5 g/L = (5 g/L)/63.546 g/mol) = 0.07868 mol/L
(a) l = 1.00 cm; c = 0.07868 mol/L; A = 3.500 = cl
So,  = (3.5) / [(0.07868 mol/L)(1 cm)] = 44.484 Lmol-1cm-1
(b) l = 1.00 cm; c = 0.07868/2 mol/L;  = 44.484 Lmol-1cm-1
So, A = cl = 1.75
Transmittance, T = 10-A = 10-1.75 = 0.0178

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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.

Sol. IR band around 1700 and 2700 cm-1 is indication of an aldehyde group.
In NMR spectrum, peaks between 6.5 and 8 are indication of 4 aromatic protons that show
splitting because of their neighboring protons. Peak above 10 is indication of highly
deshielded proton such as aldehyde proton attached to a benzene. Singlet around 2.5 for three
protons is due to a methyl group that does not undergo any splitting.

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)
Sol. IHD = 4, so it could be a substituted benzene
Broad peak around 3400 in IR is indication of OH group.
In NMR, peak between 6.5 to 8 indicates benzene, singlet at 2.2 is for methyl and 4.6 for two
protons could be for deshielded methylene protons. Peak at 5.3 is corresponding to the OH
group.

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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).
Sol. Singlet at 3.38 could be methyl bonded to an electronegative atom. Multiplet around 3.53
for four protons could be due to two CH2 groups adjacent to each other and triplets at 3.82
and 3.59 indicate CH2 groups attached to electronegative atoms. Since oxygen is more
electronegative than Br, peak at 3.82 is corresponding to methylene group attached next to O
atom and triplet at 3.59 is corresponding to the CH2 group attached to Br.

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?
Sol. In the given problem, δ = 3.16, instrument frequency is 900 MHz which is equal to 900 x
106 Hertz. We need to find shift from TMS value. By using the below formula

Shift from TMS = 3.16 x 900 x 106 / 106 = 2844 Hz.

In similar manner you can find the value of chemical shift if the value of shift from TMS is
given in a question.

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.
Sol. Using the formula, ν =γB/2 , we can find the value of ν.
ν = 149.86 x 106 Hz or ~150 MHz.

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

(b)

Sol. (a) total 5 signals.

Splitting pattern for protons from left to right (n+1 rule): CH3= singlet, CH2= triplet, CH2=
quartet, CH= sextet, and CH3= doublet.

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(b) 4 singlets. (Groups attached to the same carbon atom will not split each other)
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.

Sol. IHD = 9. There could be two benzenes.

Peak around 1710 in IR is due to the presence of a carbonyl group.
In NMR, peaks between 7-8 is an indication of aromatic protons. Two triplets and one
doublet in the NMR is an indication of the following structure.

Possible structure:

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.
Ans:

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

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% Use ΔG = -RTlnK

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 (ii) (a) torsional strain (b) torsional strain and angle strain

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).
Ans:

(ii)

There are two 1,3 diaxial interactions which gives energy of 7.6 kJ/mol in the diaxial
conformer while the equatorial conformer has no such interactions.

19. Draw the most stable chair conformation of

(i) trans-1,4-dibromocyclohexane (ii) cis-1-tert-butyl-4-methyl cyclohexane
Ans:

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

Ans: (a) and (d)

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

Ans: None

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

Ans:

23. Are these molecules chiral?

Ans: A: Chiral B: Achiral

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Ans: (a) Achiral (b) Chiral
24. Draw the possible structures for butadiene as a (i) planar compound and (ii) non planar
compound.
Ans:

25. Comment on their optical activity by considering their chair conformation.

Ans: A: Optically Inactive (plane of symmetry); B : Optically active (no plane of symmetry);
C: A: Optically Inactive (plane of symmetry); D: Optically Inactive (plane of symmetry);
26. Assign R/S for the following molecules.

Ans: (i) R (ii) R (iii)S

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

Ans: (a) R, S, (b) R, (c) R

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

Ans:

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

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: C= 0.113 gm/ml, L= 0.7 dm
Observed rotation: 76x .113x 0.7 = 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) Concentration= 0.05 gm/mL,L= 5 dm; Specific rotation= 1/(0.05 x 5) = 1/.25 = +
4o
(ii) Observed rotation = +4 x .35 x 0.5 = (+) 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.

Ans: Pure Chiral amine (the first one) as it can form a diasteromer salts that can be isolated.

29. Write the structure for the optically active compound with formulae C3I2Br2

Ans:
30. Are the following compounds meso (Yes/NO)? Provide explanation.
CH3 Br

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

CH2CH3 H

Ans: (i) NO; Substitutions are different (ii) Yes: (S)/(R) and same substituents

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31. Draw all the possible stereoisomers for this compound pent-3-en-2-ol.

Ans:
32. (a) Determine whether the two structures in each of the following pairs represent identical
compounds, constitutional isomers, or stereoisomers (enantiomers or diasteromers).

Ans: (a) Identical (b) enantiomer (c) identical (d) identical

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