Siti Nor Atika Baharin

Learning outcome
Understand the factor influence of IR absorption spectra

Solve the IR spectra problems

Factor that influence of trend in
absorption spectra
C-H

C=C

C=O
C-H stretching region
 Depends on hybridization of C-H bonds involved.
sp>sp2>sp3
Bond =C-H -C-H
Type sp sp2 sp3
Length (Å) 1.08 1.10 1.12
Strength (kJ) 506 444 422
IR frequency 3300 ~3100 ~2900
(cm-1)
examples acetylenic Vinyl aliphatic
Aromatic
cyclopropyl
C-H stretching region
 Stretching for various sp3 hybridized

Group asymmetric symmetric

methyl 2962 2872
methylene 2926 2853
methine 2890 very weak
C-H bending vibrations
 Methyl and methylene group
 in region 1465-1370 cm-1.
Methylene -CH2- scissoring band (1465 cm-1)
Methyl –CH3
1) asymmetric (1450 cm-1);
2) symmetric (1375 cm-1)
 geminal dimethyl (split into 2 (1380/1370 cm-1))
 t-butyl, (2 band wider split (1390/1370 cm-1))
Rocking band~ long chain alkanes (720 cm-1)
C-H Bending Vibrations for Alkene
 In plane and out of plane (oop) when absorb IR radiation.
 Absorption peak at 1415 cm-1 is for terminal alkenes with
scissoring in-plane vibration.
 Types:
monosubstituted , cis-1,2 disubtituted, trans-1,2-
disubstituted, 1,1-disubstituted, trisubtituted,
tetrasubstituted alkene.
C-H Bending ( for Aromatic Ring)
The out-of-plane (oop) C-H bending is useful in order to assign the
positions of substituents on the aromatic ring.

 Monosubstituted rings
this substitution pattern always gives a strong absorption near 690 cm-1.
If this band is absent, no monosubstituted ring is present. A second
strong band usually appears near 750 cm-1.

 Ortho-Disubstituted rings
one strong band near 750 cm-1.

 Meta- Disubstituted rings

gives one absorption band near 690 cm-1 plus one near 780 cm-1. A third
band of medium intensity is often found near 880 cm-1.

 Para- Disubstituted rings

one strong band appears in the region from 800 to 850 cm-1.
Ortho-Disubstituted rings

C H Bending observed as one strong band near 750 cm-1.

9
 Meta- Disubstituted rings

- gives one absorption band near 690 cm-1 plus one near 780
C H cm-1. A third band of medium intensity is often found near 880
cm-1.

10
Para- Disubstituted rings

C H - one strong band appears in the region from 800 to 850

cm-1.

11
Factor that influence of trend in
absorption spectra for C=C stretching
vibration
For acyclic alkene C=C stretch between 1670 – 1640cm-1.
# C=C frequencies increases as the alkyl group that added to
the double bond

Increase the alkyl group added to double bond

 Trans-disubstituted
Tetrasubstitutional
alkenes (higher
Intensity (weaker), (weaker & not
frequencies 1670 cm-1)
compared to C=O observed)-due to less
than cis-disubstituted
dipole moment
alkene (1658 cm-1).

Absorption of cis-alkene
which is less symmetry In ring often symmetric
(higher), than trans- (weaker), compared to
alkene (weaker) due to long chain (higher)
less dipole moment
Factor that influence of trend in absorption
spectra for C=C stretching vibration
# Conjugation Effect
conjugation of C=C with either
C=O group or other double bond When C=C is conjugated with
causes the multiple bond showed C=O, the absorption of C=C shifts
more single-bond character (via to the lower frequency and
resonance), force contanst K intensified by strong dipole of
lowered and thus reduces the carbonyl
frequency of vibration.

_
Two absorption peaks can see due + ..
to two possible conformations C C C C C C C C

 C=C ~ 1600 cm-1

 C=C = 1630 cm-1
Factor that influence of trend in absorption spectra for
C=C stretching vibration
Ring size effects with internal double bond

• For cyclic compound, the absorption frequency

decreases as the internal angle decreases until
reaches 90o in cyclobutene but increases for
cyclopropene.

• The effect of alkyl groups attached directly to

the C=C bond in the ring on the frequency of the
absorption

 C=C (cm-1) 1650 1646 1611 1566

Ring strain increases

(angle C=C-C decreases)
"p-character" of C=C increases
Bond strength increases
Factor that influence of trend in absorption
spectra for C=C stretching vibration
 Ring size effects with external double
bond CH2
CH2
CH2
 The absorption frequency
increases when the ring size
(smaller ring) decreases.
 Smaller rings require the use of  C=C (cm-1) 1780 1678 1657
more p character to make the C-C
bonds form the requisite small CH2 CH2
CH2
angles. CH2
 The p character from the sigma
bond of the C=C bond is removed
/reduced which gives more s
 C=Cstrengthen
character and (cm-1) 1780the C=C1678 1657 1651
bond.
 The value of force constant K
increased thus increases the
absorption frequency.
 Carbonyl compounds (C=O)
 The aldehydes, ketones, acids, esters, amides, acid chloride and
anhydrides groups contain C=O (carbonyl) group
 This group absorbs strongly in the range from 1850 to 1650 cm-1:
due to large charge in dipole moment.
cm-1

1810 1800 1760 1735 1725 1715 1710 1690

Anhydride Acid Chloride Anhydride Ester Aldehyde Ketone Carboxylic acid
Amide
(band 1) (band 2)

Normal base values for the C=O stretching vibrations for carbonyl
groups.
Carbonyl compounds (C=O)
 The range of values given can be explained through:

1. Inductive effect 3. Hydrogen bonding

2. Resonance effect
1st and 2nd effect
influence to the C=O
strength frequency
Carbonyl compounds (C=O)
Inductive Effect

Positive Inductive Effect (electron donating effect):

Introduction of alkyl group causes positive inductive effect which
gives rise to the lengthening or weakening of the bond. Due to this
absorbance takes place at lower wave number.

Eg. C=O
i) Formaldehyde (HCHO) 1750cm-1
ii) Acetaldehyde (CH3CHO) 1745cm-1
iii) Acetone (CH3COCH3) 1715cm-1
 Carbonyl compounds (C=O)
Negative Inductive Effect (electron withdrawing effect):
Similarly introduction of electronegative atom or groups tend to draw
in the electrons between C and O (electron withdrawing effect), C=O
become stronger increases the wave number of absorbance.
Element with has electronegativity > O (or same)

i) Acetone (CH3COCH3) 1715cm-1

ii) Chloroacetone (ClCH2COCH3)
iii) Dichloroacetone (Cl2CHCOCH3)
1725cm-1 Ester<acid chloride<
1740cm-1 anhydride
# anhydride has 2 peaks
due to symmetric &
asymmetric vibrational
Carbonyl compounds (C=O)
How about amide, with the present of N?
N atom is less electronegative than the oxygen atom
N has unpaired electron.
Benzamide
(C=O)
RESONANCE EFFECT: 1663cm-1
Unpaired electron more labile
conjugated with C=O, resulting in
increasing of single bond character &
lowering the C=O absorption
frequency
Phenyl acetate
(C=O)
1730cm-1
Carbonyl compounds (C=O)

-ve
Carbonyl compounds (C=O)
 How about Carboxylic acid group?
 COOH, it has O which give electron withdrawing effect.
 But why the IR absorbtion frequency is lower than ester?

Hydrogen bonding:
-COOH exist in monomeric form in
very diluted solution
-in concentrated solution tend to
dimerize via hydrogen bonding
-weakens the C=Obond, lower the K,
lower in frequency
Factors That Influence the C=O
Stretching Vibration

Conjugation effects Ring size effects

Hydrogen bonding
Substitution effects
effects
Factors That Influence the C=O
Stretching Vibration
1. Conjugation effects

The alternate C=C and C=O resulting delocalization of π

electrons in C=C and C=O.

This conjugation effect increases the single-bond character

of C=C and C=O bonds in the resonance hybrid and thus
lower the force constant, K and lowering the values of
absorption frequencies.

For two possible conformations; s-cis and s-trans: The s-cis

conformation shows higher absorption frequency rather then
s-trans
Factors That Influence the C=O
Stretching Vibration
2. Ring-Size Effects

Decreasing the ring size increases the absorption frequency

of C=O. The smaller rings require the use of more p character
to make the C-C form the requisite small angles.

As a result, this removes p character of the sigma bond of

the double bond but gives more s character. Thus
strengthening the double bond and increase the force
constant, K and absorption frequency increases
Factors That Influence the C=O
Stretching Vibration
3. α-Substitution Effects
 When the neighbouring C atom of C=O is substituted with
any halogen atom such as Cl, the absorption frequency of
C=O increases. This due to the electron- withdrawing
effect. This effect strengthens the C=O. Tightening of the π
bond (shortening), increases the force constant, K leading
to the enhancement of absorption frequency.
Factors That Influence the C=O
Stretching Vibration
4. Hydrogen-Bonding effects
 Hydrogen bonding for C=O lengthens the C=O
bond and lowers the stretching force constant, K
and as a result lowering the absorption frequency
of C=O.