Infrared Spectroscopy Part 1

Lecture Supplement:
Take one handout from the stage

1
 Infrared Spectroscopy (IR)
Molecular Vibrations

Fundamental principle
Absorption of photons causes changes in molecular vibrations

Molecular Vibrations
•Bonded atoms move around in space
•Very fast: one vibration cycle ~10-15 seconds

Stretching (H-Cl) Bending (H-O-H)

•Atoms move along bond axis •Motion not along bond axis
•Less important than stretching 2
 Molecular Vibrations
Vibration energy
• ↑ vibration energy ↑ average bond length

add energy

Ground state Excited state

lower energy higher energy

3
 Molecular Vibrations
Vibration energy
• Vibrational energy is quantized (only certain energy values are possible)
Vibrational state energy

Excited vibrational state

∆ E = hν ν = stretching frequency

Ground vibrational state

For bond vibrations:

∆ Ε = dependent on bond
= ~5 kcal mol-1
= lower energy than red light photons
= infrared photons
4
 The Infrared Spectrum
Spectrum = plot of photon energy versus photon quantity
Typical infrared spectrum:
Number of photons absorbed

Few
photons
absorbed

Many photons absorbed

Stretching frequency
Proportional to photon energy
5
 Molecular Structure from IR Spectrum
How does spectrum give information about molecular structure?
•Structure controls number of photons absorbed
•Structure controls stretching frequency

6
 Structure versus Photon Quantity
From quantum mechanics:

Chance of photon absorption controlled by change in dipole moment (µ )

Intensity of IR peak Vector sum of bond dipoles

δ +X Yδ -
Useful approximation
Consider only one bond

7
 Absorption Intensity versus Bond Dipoles
δ +
X Yδ -

•Bond dipole ~ (magnitude of electronegativity difference) x (bond length)

• ↑ ∆ EN ↑ dipole
• ↑ bond length ↑ dipole
• ↑ bond dipole ↑ absorption

In practical terms:
•Highly polar bond → strong peak
•Symmetrical (nonpolar) or nearly symmetrical bond → peak weak or absent

8
 Absorption Intensity versus Bond Dipoles
O

Examples: C=O peak strong

H3C CH3

H3C CH3

C=C peak absent (or maybe weak)

H3C CH3

H H

C=C peak present but weak

H3C CH3

Caution!
•Weak peaks not always discernable
•Be careful when excluding symmetrical functional groups base on absence of peak
9
 Structure versus Stretching Frequency
Hooke’s Law (1660)
•Stretching frequency of two masses on a spring
atoms bond

spring stiffness → bond order

mA + mB 1/2 C-C
1
increasing
Stretching frequency =
2πc
f
mAmB C=C stretching frequency
C≡ C
atom masses

Functional groups determine IR stretching frequencies

10
 Characteristic Stretching Frequencies
The Five Zones
IR spectrum divided into five zones (groups) of important absorptions

1 2 3 4 5 Fingerprint region

11
 Characteristic Stretching Frequencies
The Five Zones

Bond Stretching Frequency Shape and Intensity

Zone 1: 3700-3200 cm-1

Alcohol O-H 3650-3200 cm-1 usually strong and broad

Alkyne ≡ C-H 3340-3250 cm-1 usually strong and sharp
Amine or amide N-H 3500-3300 cm-1 medium; often broad
Zone 2: 3200-2700 cm-1

Aryl* or vinyl** sp2 C-H 3100-3000 cm-1 variable

Alkyl sp3 C-H 2960-2850 cm-1 variable
Aldehyde C-H ~2900, ~2700 cm-1 medium; two peaks
Carboxylic acid O-H 3000-2500 cm-1 usually strong; very broad

* attached to benzene ring **attached to alkene 12

 Characteristic Stretching Frequencies
The Five Zones

Bond Stretching Frequency Shape and Intensity

Zone 3: 2300-2000 cm-1

Alkyne C≡ C 2260-2000 cm-1 sharp and variable

Nitrile C≡ N 2260-2220 cm-1 sharp and variable
Zone 4: 1850-1650 cm-1

Ketone C=O 1750-1705 cm-1 strong

Ester C=O 1750-1735 cm-1 strong
Aldehyde C=O 1740-1720 cm-1 strong
Carboxylic acid C=O 1725-1700 cm-1 strong
Amide C=O 1690-1650 cm-1 strong

C=O frequencies 20-40 cm-1 lower when conjugated to a pi bond 13

 Characteristic Stretching Frequencies
The Five Zones

Bond Stretching Frequency Shape and Intensity

Zone 5: 1680-1450 cm-1

Alkene C=C 1680-1620 cm-1 variable

Benzene C=C ~1600 and variable;
1500-1450 cm-1 1600 cm-1 often two peaks

•Complete table: Thinkbook, inside front cover

What do I have to know?

•Functional groups in each zone → Learn by working lots of problems
•Do not memorize stretching frequencies; memorize the zones; frequencies
always change with the environment of the bond
14
Guided Tour of Functional Groups
Terminal Alkyne

C-C

H C C CH2CH2CH2CH3

15
Guided Tour of Functional Groups
Terminal Alkene

H C
C CH2CH2CH2CH3
16
H
Guided Tour of Functional Groups
Alcohol

broad

C-O

H O CH2CH2CH2CH2CH2CH3

17
Guided Tour of Functional Groups
Ketone

very strong

1718 cm-1

C
H3C CH2CH3
18
Infrared Spectroscopy Part 2

Lecture Supplement:
Take one handout from the stage

19
 Infrared Spectroscopy Part 1 Summary
•Infrared photons cause excitation of molecular vibrations
•Photon absorption probability higher with more polar bonds
•Energy of photons absorbed depends on:
Bond order
Masses of atoms bonded } Functional groups
•IR spectrum divided into five zones
•Each zone analyzed for absence or presence of functional groups
•Stretching frequency, peak shape both important
Alcohol O-H usually gives broad peak
C=O stretch gives strong peak

20
Guided Tour of Functional Groups
Ketone (again)

very strong

1718 cm-1

C
H3C CH2CH3
21
 Guided Tour of Functional Groups
Aldehyde

very strong
~2900 cm-1
usually obscured 1718 cm-1

C
H CH2CH2CH2CH2CH3
22
Guided Tour of Functional Groups
Ketone with Alkene Conjugation

1720 cm-1

O H
Conjugation with pi bond lowers
C C C=O stretch by 20-40 cm-1
H3C C H
23
H
Guided Tour of Functional Groups
Ester

1743 cm-1

C
CH3O CH2CH2CH2CH2CH3
24
Guided Tour of Functional Groups
Carboxylic Acid

very broad

1711 cm-1

H C
O CH2CH2CH2CH2CH3
25
Guided Tour of Functional Groups
Benzene Ring

May be two peaks

H H

H 3C H

H H

26
 Five Zone IR Spectrum Analysis
Example #1: C6H12 O2

1700 cm-1

Step 1: Calculate DBE

DBE = C - (H/2) + (N/2) + 1
= 6 - (12/2) + (0/2) +1
=1
One ring or one pi bond

27
 Five Zone IR Spectrum Analysis
Example #1: C6H12 O2

1700 cm-1

Step 2: Analyze IR Spectrum

•Zone 1 (3700-3200 cm-1 )
Alcohol O-H: Present
N-H: Absent - no N in formula
≡ C-H: Absent - not enough DBE

28
 Five Zone IR Spectrum Analysis
Example #1: C6H12 O2

1700 cm-1

•Zone 2 (3200-2700 cm-1 )

Aryl/vinyl sp2 C-H: Probably not (not enough DBE)
Alkyl sp3 C-H: Present
Aldehyde C-H: Absent - no 2700 cm-1
Carboxylic acid O-H: Absent - not broad enough

29
 Five Zone IR Spectrum Analysis
Example #1: C6H12 O2

1700 cm-1

•Zone 3 (2300-2000 cm-1 )

Alkyne C≡ C: Absent - no peaks; not enough DBE
Nitrile C≡ N: Absent - no peaks; not enough DBE

30
 Five Zone IR Spectrum Analysis
Example #1: C6H12 O2

1700 cm-1

•Zone 4 (1850-1650 cm-1 )

C=O: Present @ 1700 cm-1
Possibilities: ketone
ester - not enough oxygens
aldehyde - no 2700 cm-1 peak
carboxylic acid - zone 2 not broad
amide - no nitrogen
31
 Five Zone IR Spectrum Analysis
Example #1: C6H12 O2

1700 cm-1

•Zone 5 (1680-1450 cm-1 )

Benzene ring: Absent - no peak ~1600 cm-1 ; not enough DBE
Alkene C=C: Absent - no peak ~1600 cm-1 ; not enough DBE
O OH
Actual structure:

32
 Five Zone IR Spectrum Analysis
Example #2: C8H7N

Step 1: Calculate DBE

DBE = C - (H/2) + (N/2) + 1
= 8 - (7/2) + (1/2) +1
=6
Six rings and/or pi bonds
Possible benzene ring
33
 Five Zone IR Spectrum Analysis
Example #2: C8H7N

Step 2: Analyze IR Spectrum

•Zone 1 (3700-3200 cm-1 )
Alcohol O-H: Absent - no oxygen in formula
N-H: Absent - peaks too small
≡ C-H: Absent - peaks too small

34
 Five Zone IR Spectrum Analysis
Example #2: C8H7N

•Zone 2 (3200-2700 cm-1 )

Aryl/vinyl sp2 C-H: Present - peaks > 3000 cm-1
Alkyl sp3 C-H: Present - peaks < 3000 cm-1
Aldehyde C-H: Absent - no 2700 cm-1 ; no C=O in zone 4
Carboxylic acid O-H: Absent - not broad enough; C=O in zone 4

35
 Five Zone IR Spectrum Analysis
Example #2: C8H7N

•Zone 3 (2300-2000 cm-1 )

Alkyne C≡ C: Possible
Nitrile C≡ N: Possible }

36
 Five Zone IR Spectrum Analysis
Example #2: C8H7N

•Zone 4 (1850-1650 cm-1 )

C=O: Absent - no peak; no oxygen in formula

37
 Five Zone IR Spectrum Analysis
Example #2: C8H7N

•Zone 5 (1680-1450 cm-1 )

Benzene ring: Present - peaks ~1600 cm-1 and ~1500 cm-1
Alkene C=C: Absent - not enough DBE for alkene plus benzene plus
triple bond

Actual structure: CH2C N

38