Exercise

42. List three factors that influence the intensity of an IR

absorption band.
Solution:
1. Change in the dipole moment
2. Concentration of sample
3. No of bonds that causes the absorption band

44. Rank the following compounds in order of increasing λmax:

Solution:
The increasing order is C < B < A < D

➢ More the conjugation , longer the wavelength.

45. For each of the following pairs of compounds, identify one IR

absorption band that could be used to distinguish between them:

A.

Solution:
(i) In ester, there is electron withdrawing group attached that increases the
double bond character so the C=O group band appears at 1735 cm-1
while in ketone there are 2 electron donating group that increases the
single bond character so the C=O band appear at 1715 cm-1
(ii) Main reason: In ester, there is C-O absorption band that appears at
approx. 1200 while in ketone C-O absorption band is absent.
 B.

Solution:
An absorption band at 720 cm-1 due to in-phase rocking of the five adjacent
methylene groups would be present for heptane and absent for
methylcyclohexane.

C.
Solution:
In alcohol, there would be present absorption of band at 3400-3200 cm-1 due to
OH group while in ether, it would be absent.

D.
Solution:
(i) In amide, absorption of band occur at 3400-3200 cm-1 due to N-H while
in ester, it would be absent.
(ii) In ester, C-O absorption of band occur at approximately 1200 cm-1
while in amide, there is no C-O absorption of band

E.
Solution:
In second alcohol, methyl group is present so absorption of band appears at 1375
cm-1 while In primary alcohol, methyl group is absent so the absorption of band
for CH3 bend is absent.

F.
Solution:
A weak C=C absorption of band at 1660-1600 cm-1 would be present for the cis
isomer and absent for the trans isomer, since only the trans isomer is symmetrical.

G.

Solution:
In ester, C=O band absorption occur at 1735 cm-1 due to presence of electron
withdrawing group while In ketone, C=O band absorption occur at 1720 cm-1 due
to presence of two electron donating group with a electron withdrawing group.

H.

Solution:
In 3-cyclohexenone, C=O band absorption occur at 1715 cm-1 while In 2-
cyclohexenone, C=O band absorption occur at 1690 cm-1 due to double bond is
in conjugation with C=O.

I.
Solution:
(i) In 2-pentene, sp2 C-H band absorption occur at 3090-3010 cm-1 while
In 2-pentyne, sp C-H band absorption occur at 3300cm-1.
(ii) In 2-pentene, C=C band absorption occur at 1660-1600 cm-1 while In 2-
pentyne, C≡C band absorption occur at 2150 cm-1.
 J.
Solution:
(i) In aldehyde, band absorption occur at 2800-2700 cm-1 due to aldehyde
C-H stretching band while In ketone, that band absorption will be
absent.
(ii) In aldehyde, C=O band absorption occur at 1725 cm-1 due to presence
of one electron donating group while in ketone, C=O band absorption
occur at 1715 cm-1 due to presence of two electron donating group.

K.

Solution:
(i) In Cyclohexanal, band absorption occur at 3000-2840 cm-1 due to
presence of sp3 C-H while In benzaldehyde, band absorption occur at
3100-3020 cm-1 due to presence of aromatic C-H stretching band.
(ii) In benzaldehyde, aromatic C=C band absorption occurs at 1600 cm-1
and 1500cm-1 while in Cyclohexanal, that absorption is absent.

46. (a) How could you use IR spectroscopy to determine whether

the following reaction had occurred?
(b) After purifying the product, how could you determine
whether all the NH2NH2 had been removed?
Solutions:
(A) When the reaction occur, C=O band absorption at 1700 cm-1 and
aldehyde C-H band absorption at 2800-2700 cm-1 of reactant
decreases as the reaction proceed. If all the aldehyde used up then
both the band absorption will disappear.
(B) If all the NH2NH2 are removed, there would be no N-H
absorption band at 3400-3200 cm-1

47. Assuming that the force constant is approximately the same for
C-C, C-N, and C-O bonds, predict the relative positions of their
stretching Vibrations in an IR spectrum.
Solution:
If the force constants are approximately the same, the lighter atoms will absorb
at higher frequencies.
C-C > C-N > C-O
Explanation:
Stretching frequency depends on 2 factors i.e., force constant of the bond and
reduced mass of the 2 atoms. As the force constants are same, so we have to
depend reduced mass of atom. One of the atom is same so a particular atom
increases the overall mass, the reduced mass increases and hence the frequency
(stretching wavenumber) of vibration decreases. Atomic masses of O⟩N⟩C,
therefore the reduced mass of C−O⟩C−N⟩C−C.
➢ If both the factors are not kept the same then by considering the force
constant as bond strength always play a dominant role in case of stretching
frequency.

48. Norlutin and Enovid are ketones that suppress ovulation, so

they have been used clinically as contraceptives. For which of these
compounds would you expect the infrared carbonyl absorption
(C=O stretch) to be at a higher frequency? Explain.
Solutions:
Envoid have to be at higher frequency then Norlutin because In
norlutin, band absorption occurs at 1690 cm-1 due to the presence of
conjugation that reduces its frequency.

49. In the following boxes, list the types of bonds and the
approximate wavenumber at which each type of bond is expected
to show an IR absorption:
Solutions:
3600 3000 1800 1400 1000
OH (3400-3200) sp3 C-H (3000- C=O (1800- C-O (1200-
2840) 1600) 1100)
N-H (3400-3200)
Aldehyde C-H
sp C-H (3300) (2800-2700)
C=C (1660-
1600) C-N (1230-
sp2 C-H (3090- C≡C (2150) 1030)
3010) Aromatic C=C
C≡N (2250) (1500)
Wavenumber (cm-1)
51. How could IR spectroscopy distinguish between 1,5-hexadiene
and 2,4-hexadiene?
Solution:

1,5-hexadiene 2,4-hexadiene
Explanation:
(i) In 1,5-hexadiene, there will be no band absorption occur at 1375 cm-1
due to absence of CH3 bend while in 2,4-hexadiene, there will band
absorption at 1375 cm-1 due to CH3 bend.
(ii) In 1,5-hexadiene, there is no conjugated double bond character that adds
the single bond character while in 2,4-hexadiene, there is double bond
conjugation that increases the single bond character that’s why C=C
band in 1,5-hexadiene will be at higher wavenumber then 2,4-
hexadiene.

54. The IR spectrum of a compound with molecular formula

C5H8O is shown below. Identify the compound.

Solution:

Cyclopentanone(C5H8O)

Explanation:
The following stretching of vibration are observed in IR spectrum.
 Present Absent
OH(alcohol) (3400-3200)
Aliphatic C-H (3000-2840) OH(acid) (3400-2400)
NH (3400-3200)
C=O (1745-1700) sp C-H (3300)
2
sp C-H (3090-3010)
CH2 bend (1465) Aldehyde C-H (2800-2700)
C≡C (2150)
C≡N (2250)
C=C (1660-1600)
C-O (1300-1000)
C-Cl (730-550)

The presence of Aliphatic C-H and C=O band confirms the ring and carbonyl
compounds (Aldehyde, ketone, ester, carboxylic acid, amide, acid chloride and
anhydride).
• Absence of OH(acid) band confirms that it is not carboxylic acid.
• Absence of NH2 band confirms that it is not amide.
• Absence of Aldehyde C-H confirms that it is not aldehyde.
• Absence of C-O band confirms that it is not ester and anhydride.
• Absence of C-Cl band confirms that it is not acid chloride.
• The absorption of C=O at 1745 confirms the Cyclopentanone due to
ring strain.

55. Rank the following compounds from highest wavenumber to

lowest wavenumber for their C=O absorption band:

A B C
Solution:
➢ Less the electron donating group attached to the C=O, higher will be the
wavenumber.
From higher wavenumber to lower wavenumber: B > C > A.
 • In formaldehyde, there is no electron donating group.
• In acetaldehyde, there is one electron donating group.
• Acetone, there are two electron donating group.
59. Which one of the following five compounds produced the IR
spectrum shown below?

Solution:

Explanation:
• Band absorption at 3400-3200 cm-1 confirms the alcoholic OH group. So
it can be phenol, benzyl alcohol, cyclohexylmethanol, 1-cyclohexyl-2-
hydroxyethanone. For benzoic acid, band absorption have to be at 3400-
2400 cm-1 for OH (acid).
• Band absorption at 3090-3010 cm-1 confirms the sp2 C-H. It confirms that
may be phenol. Absence of sp3 C-H band absorption confirms the absence
of benzyl alcohol, cyclohexylmethanol, 1-cyclohexyl-2-hydroxyethanone.
• Absence of C=O band absorption further confirms the absence of benzoic
acid and 1-cyclohexyl-2-hydroxyethanone.
• Band absorption at 1600 and 1500 cm-1 due to aromatic C=C and band
absorption at 1200-1100 cm-1 due to C-O confirms the phenol.
60. The IR spectrum of compound A with a molecular formula of
C5H12O is shown below. Compound A is oxidized to give compound
B, a ketone with a Molecular formula of C5H10O. When compound
A is heated with H2SO4,compoound C and D obtained.
Considerably more D is obtained than C. Reaction of compound C
with O3, followed by treatment with dimethyl sulfide, gives two
products: formaldehyde and compound E, with a molecular
Formula of C4H8O. Reaction of compound D with O3, followed by
treatment with dimethyl sulfide, gives two products: compound F,
with a molecular Formula of C3H6O, and compound G, with a
molecular formula of C2H4O. What are the structures of A through
G?

Solution:

Pentan-2-ol (C5H12O)
Explanation:
Through IR spectrum
• Band absorption at 3400-3200 cm-1 due to OH group in
C5H12O.
• Band absorption at 3000-2840 cm-1 due to the sp3 C-H in
C5H12O confirms the unsaturated alcohol with 5 carbon
atom.
• There is no ispropyl band absorption at 1370 cm-1 like
shown in figure.
• The band absorption at 1465 cm-1 and 1375 cm-1 due to
CH2 and CH3 bend in which both the bands are almost
equal in size indicates it may be 2-pentanol or 3-pentanol.
Through Reactions
• When compound A is heated with H2SO4 have to produce compound C and
D since Pentan-3-ol would form just pent-2-ene, it is clear that the structure
of A must be an asymmetrical alcohol. Pentan-2-ol would form pent-1-ene
and pent-2-ene (major due to more substituted alkene).
• The structure of compound through A to G shown in the reaction is given:
61. Each of the IR spectra shown below is accompanied by a set of
four compounds. In each case, indicate which of the four
compounds is responsible for the spectrum.

Solution:

1-hexene
Explanation
• Band absorption at 2150 cm-1 indicate the C≡C which confirms that it may
be 1-hexene or 2-hexene.
• Absence of OH and C=O band absorption at 3400-3200 cm-1 and 1745-
1700 cm-1 confirms that there are not alcohol and carboxylic acid.
• Band absorption at 3300 cm-1 indicate the sp C-H that confirms it is 1-
hexene while there will be no band absorption at 3300 cm-1 in 2-hexene
due to the absence of Hydrogen with sp hybridized carbon.
Solution:

Ethyl propionate
Explanation:
• Absence of OH and aldehyde C-H band absorption at 3400-2400 cm-1 and
2800-2700 cm-1 confirms the absence of carboxylic acid and aldehyde.
• C=O band absorption at 1745-1700 cm-1 confirms it is whether ester or
Ketone.
• C-O absorption of band at 1200-1100 cm-1 confirms that it is ester.
Solution:

Tert-butyl benzene

Explanation:
• Absence of band absorption at 3400-3200 cm-1 confirms there is
no OH group. So this spectrum is not for benzyl alcohol.
• Band absorption at 3050-3010 cm-1 due to presence of aromatic
sp2 C-H confirms the aromaticity.
• Band absorption at 1375 cm-1 with splitting band into two peaks
due to presence of Tert-butyl confirms the Tert-butyl benzene.

62. Five compounds are shown for each of the IR spectra below.
Indicate which of the five compounds is responsible for each
spectrum.
Solution:

n-butanol
Explanation:
• OH band absorption at 3400-3200 cm-1 confirms the presence of alcohol.
• Absence of sp2 C-H band absorption at 3090-3010 cm-1 confirms the
absence of alkene and unsaturated alcohol.
• Sp3 C-H band absorption at 3000-2840 cm-1 confirms the saturated alcohol.
• Band absorption at 1465 cm-1 and 1375 cm-1 due to CH2 and CH3 bend.
• C-O band absorption at 1300-1000 cm-1 confirms the n-butanol.

Solution:

Acetophenone
Explanation:

• Aromatic C=C band absorption at 1600 cm-1 and 1500 cm-1

confirms the aromaticity.
 • Absence of OH(acidic & alcoholic) band absorption at 3400-2400
cm-1(acidic) and 3400-3200 cm-1(alcoholic) confirms that
carboxylic acid and benzyl alcohol are absent.
• Absence of aldehyde C-H band absorption at 2800-2700 cm-1
confirms that aldehyde is absent.
• Band absorption at 1690 cm-1 confirms that C=O is conjugated.
So it is Acetophenone.

63. A compound is known to be one of those shown here. What

absorption bands in its IR spectrum allow you to identify the
compound?

Solution:
Compound A:
• Aldehyde C-H band absorption occur at 2800-2700 cm-1.
• CH3 bend absorption of band will be absent at 1375 cm-1 due to absence
of methyl group.
Compound B:
• Absorption of band occurs at 1375 cm-1 for CH3 bend due to presence of
methyl group.
• Absorption of band at 2800-2700 cm-1 will be absent due to absence of
aldehyde C-H stretch.
Compound C:
• Aldehyde C-H band absorption occur at 2800-2700 cm-1.
• Absorption of band occurs at 1375 cm-1 for CH3 bend due to presence of
methyl group.
64. How can IR spectroscopy distinguish between 1-hexyne, 2-
hexyne, and 3-hexyne?
Solution:

1-hexyne
• Band absorption at 3300 cm-1 for sp C-H.
• Band absorption at 2150 cm-1 due to C≡C.

2-hexyne
• No band absorption at 3300 cm-1 for sp C-H due to no hydrogen is attached
with sp carbon.
• Band absorption at 2150 cm-1 occur due to C≡C.

3-hexyne
• There will be neither the band absorption at 3300 cm-1 nor band absorption
at 2150 cm-1 as there is no change in dipole moment due to symmetry.

67. Give approximate wavenumbers for the major characteristic

IR absorption bands that would be given by each of the following
compounds:

A.
Solution:
• Aldehyde C-H 2800-2700 cm-1
• C=O 1725 cm-1
• C=C 1660-1600 cm-1
 B.
Solution:
• C=O 1715 cm-1
• C-O 1300-1000 cm-1
• Aromatic C=C 1600 and 1500 cm-1

C.

Solution:
• OH 3400-3200 cm-1(broad)
• C-O 1300-1000 cm-1

D.
Solution:
• C=O 1715 cm-1
• N-H 3400-3200 cm-1
• C-N 1350-1000 cm-1

F.

Solution:
• C=O 1710 cm-1
• OH(acidic) 3400-2400 cm-1(broad)
 • C-O 1300-1000 cm-1

69. Which one of the following five compounds produced the IR

spectrum shown below?

Solution:

Benzyl alcohol
Explanation:
• OH band absorption occur at 3400-3200 cm-1.
• sp2 C-H band absorption occur at 3050-3010 cm-1.
• sp3 C-H band absorption at 3000-2840 cm-1.
• Aromatic C=C band absorption at 1600 and 1500 cm-1.
• C-O band absorption at 1300-1000 cm-1 confirms the benzyl alcohol.
71. Each of the IR spectra shown below is the spectrum of one of
the following compounds. Identify the compound that produced
each spectrum.

Spectrum A

Solution:

Explanation:
• sp3 C-H band absorption at 3000-2840 cm-1.
• Aldehyde C-H band absorption at 2800-2700 cm-1.
• C=O absorption of band at 1725 cm-1.
 Spectrum B

Solution:

Explanation:
• N-H band absorption at 3400-3200 cm-1.
• sp3 C-H band absorption at 3000-2840 cm-1.
• C=O band absorption at 1690 cm-1.
• C-N band absorption at 1350-1000 cm-1.

Spectrum C
Solution:

Explanation:
• Aliphatic C-H band absorption at 3000-2840 cm-1.
• C=O band absorption absorption at 1715 cm-1.
• C-O band absorption at 1300-1000 cm-1.