Chem 533 Lec03 PDF

CHEM-533: Organic Spectroscopy
CHEM-533
Session
03
Jan 24, 2023
Dr. Rahman S. Z. Saleem
Instrumentation: Dispersive IR
2
Instrumentation: Dispersive IR
3
Instrumentation
𝐼s
The resultant graph is a percent transmittance (%T) = x 100
𝐼r
5
IR spectrograph show the %age transmittance
Sample preparation
Most often the organic compound is liquid or solid
a glass or plastic cell is not good.
Why?
Glass or plastic absorb too strongly in IR region
Nujol Mull: Mineral Oil (It is a heavy paraffin oil)
Generally cell is made of ionic substances: NaCl, KBr,
Nujol (a brand of mineral oil- a heavy paraffin oil)6

Sample preparation
Material Transparent Ranges (cm-1) Solubility Notes
NaCl 40,000 – 625 H2 O Easy to polish, hygroscopic
Silica glass 55,000 – 3,000 HF Attacked by HF
Quartz 40,000 – 2,500 HF Attacked by HF
Sapphire 20,000 – 1,780 - Strong
Very strong, expensive, hard,
Diamond 40,000 – 2,500 and 1,800 - 200 -
useless for pellets.
Attacked by acids, avoid
CaF2 70,000 – 1,110 Acids
ammonium salts.
BaF2 65,000 – 700 - Avoid ammonium salts
ZnSe 10,000 – 550 Acids Brittle, attacked by acids
AgCl 25,000 – 400 - Soft, sensitive to light.
KCl 40,000 – 500 H2O, Et2O, acetone
Hygroscopic, soft, easily polished,
KBr 40,000 – 400 H2O, EtOH
commonly used in making pellets.
CsBr 10,000 – 250 H2O, EtOH, acetone Hygroscopic, soft.
H2O, EtOH, MeOH,
CsI 10,000 – 200 Hygroscopic, soft.
acetone
Teflon 5,000 - 1,200, 1,200 – 900 - Inert, disposable
4,000 - 3,000, 2,800 - 1,460, 1,380
Polyethylene - Inert, disposable 7
- 730, 720 - 30
Sample preparation
Nujol Mull (for solids) Neat (for liquids)

sample+org. solvent (for solids)
8
Sample preparation
9
Sample preparation
Fun fact: We do not need to do this at all
Because we will use the
spectrophotometer does not
require such sample prep
KBr pallet (for solids)
10
The instrument that we have is ATR-IR
11
The instrument that we have is Attenuated Total Reflection-IR
12
The instrument that we have is Attenuated Total Reflection-IR
The instrument also has option to compare our spectrum to spectral library that came with the
instrument
13
What to look for when examining infrared spectra
~2973cm-1 1710cm-1
C-H stretch C=O & C-C stretch region
14
So the IR spectrum looks something like
Single bond stretch Triple bond Double bonds Single bonds and finger print region
C-H C-O
C=O
strech C-N
O-H, N-H CΞN C=C
C-C
strech CΞC C=N
bending rocking
15
Typical Infrared Absorption Frequencies

A Simplified Infrared Correlation Chart
Type of Vibration Frequency (cm-1) Intensity
C-H Alkanes (stretch) 3000-2850 s

-CH3 (bend) 1450 and 1375 m
-CH2- (bend) 1465 m
Alkenes (stretch) 3100-3000 m
(out-of-plane bend) 1000-650 s
Aromatics (stretch) 3150-3050 s
(out-of-plane bend) 900-690 s
Alkyne (stretch) ~3300 s
Aldehyde 2900-2800 w
2800-2700 w
C-C Alkane not interpretatively useful
C=C Alkene 1680-1600 m-w
Aromatic 1600 and 1475 m-w
C≡C Alkyne 2250-2100 m-w
C=O Aldehyde 1740-1720 s
Ketone 1725-1705 s
Carboxylic Acid 1725-1700 s
Ester 1750-1730 s
Amide 1670-1640 s
Anhydride 1810 and 1760 s
Acid Chloride 1800 s
C-O Alcohols, Ethers, Esters, Carboxylic Acids, Anhydrides 1300-1000 s
17
Typical Infrared Absorption Frequencies

A Simplified Infrared Correlation Chart
Type of Vibration Frequency (cm-1) Intensity
O-H Alcohols, Phenols

Free 3650-3600 m
H-bonded 3500-3200 m
Carboxylic Acids 3400-2400 m
N-H Primary and Secondary Amines and Amides
(stretch) 3500-3100 m
(bend) 1640-1550 m-s
C-N Amines 1350-1000 m-s
C=N Imines and Oximes 1690-1640 w-s
C≡N Nitriles 2260-2240 m
X=C=Y Allenes, Ketenes, Isocyanates, Isothiocyanates 2270-1950 m-s
N=O Nitro (R-NO2) 1550 and 1350 s
S-H Mercaptans 2550 w
S=O Sulfoxides 1050 s
Sulfones, Sulfonyl Chlorides, Sulfates, Sulfonamides 1375-1300 and ss
1200-1140
C-X Fluoride 1400-1000 s
Chloride 800-600 s
Bromide, Iodide <667 s
18
How to approach analysis of a spectrum

For an unknown compound
Concentrate first on presence of absence of few major functional groups (-C=O, O-H,
N-H, C-O, C=C, C≡C, C≡N, NO2 are most conspicuous and give immediate
information).
Almost all compounds have C-H absorption near 3000cm-1.
19

1- Is carbonyl group present? Peak is often strong with medium width.
2- If carbonyl group is present, then what is its nature?
20

a- ACIDS: Is OH-group also present (broad absorption near 2400-3400cm-1)
21

b- Anhydrides: Two C=O absorption peaks near 1800 and 1760cm-1
22

c- Acid chloride: One C=O absorption peaks near 1800cm-1
23

d- AMIDES: Is NH-group also present? (medium absorption near 3400cm-1,
sometimes a double peak due to NH2)
24

e- Aldehyde: Is aldehyde C—H present? (two weak absorptions near 2850
and 2750cm-1 (right side of the C-H absorptions))
25

f- ESTERS: Is C—O also present? (strong absorption near 1300-1000cm-1)
26

f- ESTERS: Is C—O also present? (strong absorption near 1300-1000cm-1)
g- Ketone: One C=O peak and none of above peaks
27

3- If carbonyl group is absent, then:
a- ALCOHOLS, PHENOLS: broad OH absorption near 3300-3400cm-1)also
look for C—O near 1300-1000cm-1
28

b- AMINES: Medium absorption near 3400cm-1
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b- AMINES: Medium absorption near 3400cm-1
c- ETHERS: C—O strong absorption near 1300-1000cm-1
30

4- Triple bonds:
C ≡ N medium, sharp absorption near 2250cm-1
31

4- Triple bonds:
C ≡ N medium, sharp absorption near 2250cm-1
C ≡ C weak, sharp absorption near 2150cm-1
Acetylinic C ≡ C—H absorption near 3300cm-1
32

5- Double bonds or aromatic rings:
C=C weak absorption near 1650cm-1
Medium to strong absorptions in the 1600-1450cm-1 region
Aromatic and vinyl C-H bands occur left of 3000cm-1 and left of sp3 C-H region
33

6- Nitro group:
Two strong absorptions at 1600-1530cm-1 and 1390-1300cm-1
34

7- Hydrocarbons:
None of above peaks
Majority of absorption near 3000cm-1
Very simple spectrum, only other absorptions near 1600-1530cm-1
and 1390-1300cm-1
35
Next we will
• Start the survey of functional groups 𝑚1 𝑚2
36
Alkane
Survey of important functional groups: Alkanes

Generally a simpler spectrum
Four or more Bending peaks Rocking peaks

stretching peaks near near 1475- near 1475-
3000cm-1 1365cm-1 720cm-1
41
42

Asymmtertic mode generates larger dipole moment and is of greater intensity
Since several bands may appear in the C-H stretch region, it is a good idea to decide only whether the
absorptions are acetylenic (3300 cm−1), vinylic or aromatic (> 3000 cm−1), aliphatic (< 3000 cm−1), or
aldehydic (2850 and 2750 cm−1).
The C-H bending vibrations are often more useful for determining whether methyl or methylene groups
43
are
present in a molecule

The band due to –CH2 scissoring is usually at 1465 cm-1
One of the bands due to –CH3 bending is at 1375cm-1
(if the spectrum is simple) These two groups can be used to detect methylene and methyl group
44

In case of isopropyl (or other gem. Dimethyl groups), the 1375 cm-1 peak splits into two peaks of
equal intensity.
While splitting is more in case of t-butyl group, with peak at 1370 cm-1 being more intense than
1390cm-1 peak
45

Four or more stretching peaks near 3000cm-1
Bending peaks near 1475-1365cm-1
Rocking peaks near 1475-720cm-1
46
No 1375 cm-1 peak for cyclohexane . Why?
47

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CHEM-533: Organic Spectroscopy

a glass or plastic cell is not good.

Generally cell is made of ionic substances: NaCl, KBr,

Nujol (a brand of mineral oil- a heavy paraffin oil)6

Nujol Mull (for solids) Neat (for liquids)

KBr pallet (for solids)

The instrument that we have is ATR-IR

The instrument that we have is Attenuated Total Reflection-IR

The instrument that we have is Attenuated Total Reflection-IR

What to look for when examining infrared spectra

C-H stretch C=O & C-C stretch region

So the IR spectrum looks something like

Typical Infrared Absorption Frequencies

C-H Alkanes (stretch) 3000-2850 s

Typical Infrared Absorption Frequencies

O-H Alcohols, Phenols

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

How to approach analysis of a spectrum

• Start the survey of functional groups 𝑚1 𝑚2

Survey of important functional groups: Alkanes

Four or more Bending peaks Rocking peaks

Survey of important functional groups: Alkanes

Survey of important functional groups: Alkanes

Survey of important functional groups: Alkanes

Survey of important functional groups: Alkanes

Survey of important functional groups: Alkanes

Survey of important functional groups: Alkanes

No 1375 cm-1 peak for cyclohexane . Why?

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