Infrared Spectroscopy Part 1

Lecture Supplement: Take one handout from the stage

Midterm Exam 1
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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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) Atoms move along bond axis

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

Molecular Vibrations
Vibration energy vibration energy average bond length

add energy

Ground state lower energy

Excited state higher energy

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

Excited vibrational state DE = hn n = stretching frequency

Ground vibrational state

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

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

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Molecular Structure from IR Spectrum

How does spectrum give information about molecular structure? Structure controls number of photons absorbed Structure controls stretching frequency

Structure versus Photon Quantity

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

Absorption Intensity versus Bond Dipoles

d+ X

Y d-

Bond dipole ~ (magnitude of electronegativity difference) x (bond length) DEN 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:
H3C CH3

C=O peak strong

H3C

CH3

C=C peak absent (or maybe weak)

H3C
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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Structure versus Stretching Frequency

Hookes Law (1660) Stretching frequency of two masses on a spring atoms bond spring stiffness bond order C-C mA + mB 1/2 increasing C=C stretching frequency mAmB CC atom masses

Stretching frequency =

1 2c

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 Alkyne C-H 3650-3200 cm-1 3340-3250 cm-1 usually strong and broad usually strong and sharp

Amine or amide N-H

3500-3300 cm-1 Zone 2: 3200-2700 cm-1

medium; often broad

Aryl* or vinyl** sp2 C-H Alkyl sp3 C-H Aldehyde C-H Carboxylic acid O-H

3100-3000 cm-1 2960-2850 cm-1 ~2900, ~2700 cm-1 3000-2500 cm-1

variable variable medium; two peaks usually strong; very broad

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* attached to benzene ring **attached to alkene

Characteristic Stretching Frequencies

The Five Zones Bond Stretching Frequency Shape and Intensity

Zone 3: 2300-2000 cm-1 Alkyne CC

Nitrile CN

2260-2000 cm-1
2260-2220 cm-1 Zone 4: 1850-1650 cm-1

sharp and variable

sharp and variable

Ketone C=O Ester C=O Aldehyde C=O

1750-1705 cm-1 1750-1735 cm-1 1740-1720 cm-1

strong strong strong

Carboxylic acid C=O

Amide C=O

1725-1700 cm-1
1690-1650 cm-1

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

Characteristic Stretching Frequencies

The Five Zones Bond Stretching Frequency Shape and Intensity

Zone 5: 1680-1450 cm-1

Alkene C=C Benzene C=C 1680-1620 cm-1 ~1600 and 1500-1450 cm-1 variable 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

C-C

CH2CH2CH2CH3

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Guided Tour of Functional Groups

Terminal Alkene

H H C H C CH2CH2CH2CH3

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Guided Tour of Functional Groups

Alcohol

broad

C-O

CH2CH2CH2CH2CH2CH3

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Guided Tour of Functional Groups

Ketone

very strong

1718 cm-1

O C H3C CH2CH3

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Infrared Spectroscopy Part 2

Lecture Supplement: Take one handout from the stage

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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 Functional groups Masses of atoms bonded 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

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Guided Tour of Functional Groups

Ketone (again)

very strong

1718 cm-1

O C H3C CH2CH3

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Guided Tour of Functional Groups

Aldehyde

~2900 cm-1 usually obscured

very strong

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 H H 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 O C CH2CH2CH2CH2CH3

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Guided Tour of Functional Groups

Benzene Ring

May be two peaks

H H

H3C

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Five Zone IR Spectrum Analysis

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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Five Zone IR Spectrum Analysis

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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Five Zone IR Spectrum Analysis

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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Five Zone IR Spectrum Analysis

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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Five Zone IR Spectrum Analysis

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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Five Zone IR Spectrum Analysis

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 OH

Actual structure:
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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
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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
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Five Zone IR Spectrum Analysis

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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Five Zone IR Spectrum Analysis

Example #2: C8H7N

Zone 3 (2300-2000 cm-1) Alkyne CC: Possible Nitrile CN: Possible

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Five Zone IR Spectrum Analysis

Example #2: C8H7N

Zone 4 (1850-1650 cm-1) C=O: Absent - no peak; no oxygen in formula

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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

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