InfraredSpectroscopyPart1

LectureSupplement:
Takeonehandoutfromthestage

MidtermExam1
Date: Monday April 30
Time: 5:00-6:50 PM
Topics: Molecular Structure: Introduction and Review Carbohydrates
Location: last name A-H in Franz 1178
last name I-Sh in Haines 39
last name Si-Z in PAB 1425
Question and Answer Session
Lecture time, Monday April 30
Submit questions to harding@chem.ucla.edu
Label as Question for Q&A
Deadline for possible inclusion: noon Sunday April 29
Extra Office Hours (Steve J): Sunday 2-4 PM, Young Hall 3077F
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InfraredSpectroscopy(IR)
MolecularVibrations

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)
Atoms move along bond axis

Bending (H-O-H)
Motion not along bond axis
Less important than stretching

MolecularVibrations
Vibration energy
vibration energy average bond length

add energy

Ground state
lower energy

Excited state
higher energy

MolecularVibrations
Vibrational state energy

Vibration energy
Vibrational energy is quantized (only certain energy values are possible)
Excited vibrational state
E = h

= stretching frequency

Ground vibrational state

For bond vibrations:

= dependent on bond
= ~5 kcal mol-1
= lower energy than red light photons
= infrared photons

The Infrared Spectrum

Number of photons absorbed

Spectrum = plot of photon energy versus photon quantity

Typical infrared spectrum:

Few
photons
absorbed

Many photons absorbed

Stretching frequency
Proportional to photon energy
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MolecularStructurefromIRSpectrum
How does spectrum give information about molecular structure?
Structure controls number of photons absorbed
Structure controls stretching frequency

StructureversusPhotonQuantity
From quantum mechanics:
Chance of photon absorption controlled by change in dipole moment ()
Vector sum of bond dipoles
Intensity of IR peak
+ X
Y Useful approximation
Consider only one bond

Absorption Intensity versus Bond Dipoles

+ X

Y -

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

Absorption Intensity versus Bond Dipoles

O

Examples:

C=O peak strong

H3 C

CH3

H3 C

CH3

C=C peak absent (or maybe weak)

H3 C
H

CH3
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
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StructureversusStretchingFrequency
Hookes Law (1660)
Stretching frequency of two masses on a spring
atoms
bond

Stretchingfrequency=

1
2c

spring stiffness bond order

C-C
mA+mB 1/2
increasing
C=C stretching frequency
mAmB
CC
atom masses

Functional groups determine IR stretching frequencies

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Characteristic Stretching Frequencies

The Five Zones
IR spectrum divided into five zones (groups) of important absorptions

Fingerprint region
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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

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Characteristic Stretching Frequencies

The Five Zones
Bond

Stretching Frequency

Shape and Intensity

Zone 3: 2300-2000 cm-1

Alkyne CC

2260-2000 cm-1

sharp and variable

Nitrile CN

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

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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
1500-1450 cm-1

variable;
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; table given on exam
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Guided Tour of Functional Groups

Terminal Alkyne

CC

CH2CH2CH2CH3

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Guided Tour of Functional Groups

Terminal Alkene

H
H

C
C
H

CH2CH2CH2CH3

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Guided Tour of Functional Groups

Alcohol

broad

CO

CH2CH2CH2CH2CH2CH3

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Guided Tour of Functional Groups

very strong

Ketone

1718 cm-1

O
C
H3C

CH2CH3

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InfraredSpectroscopyPart2
LectureSupplement:
Takeonehandoutfromthestage

20

Infrared Spectroscopy Part 1 Summary

Infraredphotonscauseexcitationofmolecularvibrations
Photonabsorptionprobabilityhigherwithmorepolarbonds
Energyofphotonsabsorbeddependson:
Bondorder
Functionalgroups
Massesofatomsbonded
IRspectrumdividedintofivezones
Eachzoneanalyzedforabsenceorpresenceoffunctionalgroups
Stretchingfrequency,peakshapebothimportant
AlcoholOHusuallygivesbroadpeak
C=Ostretchgivesstrongpeak

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Guided Tour of Functional Groups

very strong

Ketone (again)

1718 cm-1

O
C
H3C

CH2CH3

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Guided Tour of Functional Groups

very strong

Aldehyde

~2900 cm-1
usually obscured

1718 cm-1

O
C
H

CH2CH2CH2CH2CH3

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Guided Tour of Functional Groups

Ketone with Alkene Conjugation

1720 cm-1
O

C
H3C

C
C
H

Conjugation with pi bond lowers

C=O stretch by 20-40 cm-1
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Guided Tour of Functional Groups

Ester

1743 cm-1

O
C
CH3O

CH2CH2CH2CH2CH3

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Guided Tour of Functional Groups

Carboxylic Acid
very broad

1711 cm-1

O
H

C
O

CH2CH2CH2CH2CH3

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Guided Tour of Functional Groups

Benzene Ring

May be two peaks

H

H3C

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FiveZoneIRSpectrumAnalysis
Example#1:C6H12O2

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
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FiveZoneIRSpectrumAnalysis
Example#1:C6H12O2

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
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FiveZoneIRSpectrumAnalysis
Example#1:C6H12O2

1700 cm-1

Zone 2 (3200-2700 cm-1)

Aryl/vinyl sp2 C-H:
Alkyl sp3 C-H:
Aldehyde C-H:
Carboxylic acid O-H:

Probably not (not enough DBE)

Present
Absent - no 2700 cm-1
Absent - not broad enough
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FiveZoneIRSpectrumAnalysis
Example#1:C6H12O2

1700 cm-1

Zone 3 (2300-2000 cm-1)

Alkyne CC: Absent - no peaks; not enough DBE
Nitrile CN: Absent - no peaks; not enough DBE

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FiveZoneIRSpectrumAnalysis
Example#1:C6H12O2

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
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FiveZoneIRSpectrumAnalysis
Example#1:C6H12O2

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

Actual structure:

OH

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FiveZoneIRSpectrumAnalysis
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
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FiveZoneIRSpectrumAnalysis
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
35

FiveZoneIRSpectrumAnalysis
Example#2:C8H7N

Zone 2 (3200-2700 cm-1)

Aryl/vinyl sp2 C-H:
Alkyl sp3 C-H:
Aldehyde C-H:
Carboxylic acid O-H:

Present - peaks > 3000 cm-1

Present - peaks < 3000 cm-1
Absent - no 2700 cm-1; no C=O in zone 4
Absent - not broad enough; C=O in zone 4
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FiveZoneIRSpectrumAnalysis
Example#2:C8H7N

Zone 3 (2300-2000 cm-1)

Alkyne CC: Possible
Nitrile CN: Possible

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FiveZoneIRSpectrumAnalysis
Example#2:C8H7N

Zone 4 (1850-1650 cm-1)

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

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FiveZoneIRSpectrumAnalysis
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

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