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Subject Chemistry

Paper No and Title 12 : Organic Spectroscopy

Module No and Title 30: Combined problem on UV, IR, 1H NMR, 13C NMR and
Mass – Part-II
Module Tag CHE_P12_M30

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Problems and their solutions

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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1. Learning Outcomes

After studying this module, you shall be able to

 Solve problem related with electronic transitions

 Learn how to differentiate molecule on the basis of IR spectroscopy
 Correlate spectra with structure of compound
 Interpret the spectroscopic data

2. Introduction

The knowledge and concepts of UV-visible, IR, 1H NMR, 13C NMR and Mass help us in
solving problems based on the experimental data. It will help us in analysing the
experimental data to elucidate the structure of any organic compound.

While analysing the data the following point must be kept in mind:

 In UV-visible spectroscopy; the types of bonds and electrons plays important role
in understanding the electronic transitions.
 UV-visible spectroscopy gives information regarding the presence of conjugation,
carbonyl group etc.
 The IR values gives information regarding the functional group present in the
molecule
 The 1H NMR tells us the number and environment of neighbouring hydrogens
present.
 The 13
C NMR helps in getting the information about the type of carbon atom(s)
present in the molecule.
 Mass spectral data gives information about the total mass and fragmentation
pattern of the molecule.

By combining all the information one can find the structure of the molecule.
CHEMISTRY PAPER No.12 :Organic Spectroscopy
MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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3. Problems and their solutions

Q.1 List all possible electronic transitions (i) CH4 (ii) CH3Br (iii) CH3COCH3 and
(iv) CH3CHO
Ans.
S. No. Compound Possible electronic transitions
(i) CH4   *
(ii) CH3Br   * & n  *
(iii) CH3COCH3 n  * ;   * & n  *
(iv) CH3CHO n  * ;   * & n  *

Q.2 The UV spectrum of acetone shows peaks at 280 nm (15) and 190 nm (100).
(i) Identify the electronic transition for each.
(ii) Which is more intense.
Ans. (i) Peaks at 280 nm (15) corresponds to n  *, whereas peaks at 190 nm (100)
corresponds to   *.
(ii)   * transition is more intense having  equal to 100.

Q.3 Why oxygen (O2), nitrogen (N2), hydrogen (H2) and chlorine (Cl2) are IR
inactive?
Ans. Oxygen (O2), nitrogen (N2), hydrogen (H2) and chlorine (Cl2) are linear in nature,
having (3N-5 = 3  2 – 5 = 1) fundamental vibrational mode of freedom, which is
symmetric stretch. Since during symmetric stretch vibration, the dipole moment of the
molecule does not change, hence this mode of vibration is IR inactive or these molecules
are IR inactive.

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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Q.4 How could you distinguish between ethanol and acetone using IR spectroscopy?
Ans.
Ethanol (CH3CH2OH) Acetone (CH3OCH3)
(i) Shows broad absorption band at 3200- (i) Broad absorption band at 3200-3550
3550 cm-1 due to O-H stretching in cm-1 due to O-H stretching in
intermolecular hydrogen-bonded alcohol intermolecular hydrogen-bonded alcohol
molecules. molecules is absent.
(ii) Shows strong absorption band at 970- (ii) Shows strong absorption band at 1060-
1250 cm-1 (usually at 1050 cm-1) due to C- 1150 cm-1 (usually at 1100 cm-1) due to C-
O stretching. O-C stretching.

Q.5 Arrange the following in the order of increasing frequency of carbonyl

absorption, giving reasons.

O O O

(I) (II) (III)

Ans. Incorporation of the carbonyl group in a small ring (5, 4 or 3-membered), raises the
stretching frequency due to the ring strain in the molecule (larger the ring strain in the
molecule, larger will be the carbonyl stretching (C=O) frequency). The carbon atom of a
carbonyl group is sp2 hybridized, which implies that the bond angles will be 120° and the
C-O sigma bond has 33% s-character. If this group is incorporated in a small ring, the C-
CO-C bond angle is reduced to 108° (5-membered ring), 90° (4-membered ring) or 60°
(3-membered ring). When this happens, the C-C bonds of the ring assume greater p-
character and the C-O sigma bond has correspondingly greater s-character. The double
bond of the carbonyl group is therefore shorter and stronger, and exhibits a larger
stretching frequency. Cyclopentanone (I) appears at 1748 cm-1, having lesser ring strain
in comparison to cyclobutanone (1783 cm-1(III)) and cyclopropane (1850 cm-1(II) having
maximum ring strain).

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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O O O

1748 cm -1 1783 cm -1 1850 cm -1

(I) (III) (II)

Q.6 How many signals are possible in cyclooctatetraene? Suggest a possible value in
ppm.

Ans: Since all the carbons are chemically and magnetically equivalent, hence
13
cyclooctatetraene will have one signal in C NMR spectrum. The possible value is 132
ppm.

Cyclooctatetraene
132 ppm

Q.7 What are the possible mass fragmentation of 4-n-butyltoluene?

4-n-butyltoluene
Ans. The benzylic bond cleavage expels the fragment of mass 43 (C3H7.; as a radical).

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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Due to McLafferty rearrangement, a neutral molecule is

expelled; propene (C3H6) with mass number 42.

Q8. A compound having molecular formula C3H6O absorbs in carbonyl reason in

IR spectrum. How can 1H NMR spectra establish that the compound is a aldehyde
or a ketone.
Ans. The molecule having molecular formula C3H6O exist in two different structural
formulas:

O O

Propanal 2-Propanone
In propanal, three signals will be obtained whereas in 2-propanone (acetone) only one
signal will be obtained.

Q9. How many signals are possible in the 13C NMR spectrum of 1-butene?
Ans. 1-Butene has molecular formula C4H8 and the structure given below.
26.3
115.1

13.7
137.3

All the four carbons are in different chemical environments and hence this molecule will
13
show 4 signals in the C NMR spectrum. The possible values in ppm is given in the
structure.

Q10. Predict the types of functional group may be inferred from the given IR spectrum.

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II
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Ans.

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.30: Combined problem on UV, IR, 1H NMR, 13C
NMR and Mass - Part II