CHY242 Chapter 15 W16

CHY242
Organic Chemistry
II
Chapter 15
Infrared Spectroscopy
& Mass Spectrometry
Amir Kiumarsi
15.1 Introduction to Spectroscopy

15.2 IR Spectroscopy
15.3 Signal Characteristics: Wavenumber
15.4 Signal Characteristics: Intensity
15.5 Signal Characteristics: Shape
15.6 Analyzing an IR Spectrum
15.7 Using IR to Distinguish between Two Compounds
15.8 Introduction to Mass Spectrometry
15.9 Analyzing the (M)+ Peak
15.10 Analyzing the (M+1) + Peak
15.11 Analyzing the (M+2) + Peak
15.12 Analyzing the Fragments
Chapter 10/2
15.14 Gas ChromatographyMass
Spectrometry
15.1 Introduction to Spectroscopy

Wavelength
Frequency
Chapter 13/3
15.1 Introduction to
Spectroscopy
There are many wavelengths of light that
cannot be observed with your eyes.
Copyright 2012 John Wiley &

Sons, Inc.
15-4
Klein, Organic Chemistry 1e
15.1 Introduction to
Spectroscopy
When light interacts with molecules, the effect
depends on the wavelength of light used.
This chapter focuses on IR spectroscopy.

Sons, Inc.
15-5
Interaction Electromagnetic Radiation

with Molecules
Chapter 13/6
Electromagnetic Spectrum
Absorption Spectra
Chapter 13/7
Electromagnetic Spectrum
Absorption Spectra
Chapter 13/8
Interaction Electromagnetic Radiation

with Molecules
p. 503
Infrared Spectroscopy
Wavenumber is the reciprocal of wavelength
Fig. 13-3, p. 505
Vibration in Organic Molecules

Vibration of Water (H2O):
http://www.youtube.com/watch?v=1uE2lvVkKW0
Vibrations of Molecules:
http://www.youtube.com/watch?v=3RqEIr8NtMI
Chapter 10/11
2012 Pearson Education, Inc.
Molecular bonds can vibrate by stretching or
by bending in a number of ways.
This chapter will focus mostly

on stretching frequencies.
Some night vision goggles
can detect IR light that is
emitted.
Sons, Inc.
15-12
The energy necessary to cause vibration
depends on the type of bond.

Sons, Inc.
15-13
In the IR spectrum:
% transmittance
Wavenumber

Sons, Inc.
15-14
IR spectrum characteristics
WAVENUMBER
INTENSITY
Strong, Moderate, weak
SHAPE

Sons, Inc.
15-15
15.3 IR Signal Wavenumber

The WAVENUMBER for a stretching vibration
depends on the bond strength and the mass
of the atoms: bonded together

Sons, Inc.
15-16

Rationalize the trends below using the
wavenumber formula:
1.
2.
Sons, Inc.
15-17

The wavenumber formula and empirical
observations allow us to designate regions as
representing specific types of bonds.

Sons, Inc.
15-18

region above 1500 cm-1 is called the diagnostic
region.
The region below 1500 cm -1 is called the

fingerprint region.
Sons, Inc.
15-19

Analyze the diagnostic and fingerprint
regions below.

Sons, Inc.
15-20

Analyze the diagnostic and fingerprint
regions below.

Sons, Inc.
15-21

Compare the IR
spectra.

Sons, Inc.
15-22

Compare the IR stretching wavenumbers below.
Are the differences due to mass or bond

strength?
Which bond is strongest, and WHY?
Sons, Inc.
15-23

Note how the region 3000 cm-1 in the IR
spectrum can give information about the
functional groups present.

Sons, Inc.
15-24

Resonance can affect the wavenumber of a
stretching signal.
Consider a carbonyl that has two resonance
contributors.
What if we have conjugation?

Sons, Inc.
15-25

conjugation
can weaken
the C=O bond
and change
the IR
absorption

Sons, Inc.
15-26
15.4 IR Signal Strength

The strength of IR signals can vary.

Sons, Inc.
15-27
15.4 IR Signal Strength

Note the general
strength of the C=O
stretching signal vs. the
C=C stretching signal.

Sons, Inc.
15-28
15.5 IR Signal Shape

Some IR signals are broad, while others are
very narrow.
OH stretching signals are often quite broad.

Sons, Inc.
15-29

Hydrogen bonds (H-bonds) also affect (weaken)
the OH bond
strength.

Sons, Inc.
15-30

In a sample with an intermediate
concentration, both narrow and broad signals
are observed. WHY?

Sons, Inc.
15-31

Primary and secondary amines exhibit NH
stretching signals. WHY not tertiary amines?
Because NH bonds are capable of Hbonding, their stretching signals are often
broadened.

Sons, Inc.
15-32

Sons, Inc.
15-33
15.6 Analyzing an IR
Spectrum
Table 15.2 summarizes some of the key
signals that help us to identify functional
groups present in molecules.
Often, the molecular structure can be
identified from an IR spectra:
1. Focus on the diagnostic region (above 1500 cm -1):
a)
b)
c)
d)
1600-1850 cm-1: check for double bonds.

2100-2300 cm-1: check for triple bonds.
2700-4000 cm-1: check for XH bonds.
Analyze wavenumber, intensity, and shape for each
signal.

Sons, Inc.
15-34
15.6 Analyzing an IR
Spectrum
Often, the
molecular
structure can be
identified from
an IR spectra:
2. Focus on the
27004000 cm-1
(XH) region.

Sons, Inc.
15-35
15.7 Using IR to Distinguish

Between Molecules
How successful is my reaction?
For the reaction below, how might IR
spectroscopy be used to analyze the reaction?

Sons, Inc.
15-38
15.7 Using IR to Distinguish

Between Molecules
For the reactions below, identify the key
functional groups, and describe how IR data
could be used to verify the formation of
product.
Is IR analysis qualitative or quantitative?

Sons, Inc.
15-39
Chapter 10/40
Fig. 13-15, p. 523
Chapter 10/41
Fig. 13-17, p. 525
Chapter 10/42
Fig. 13-19, p. 527
Chapter 10/43
Fig. 13-21, p. 528
15.8 Introduction to Mass

Spectrometry
Mass spectrometry (MS) is primarily used to
determine the molar mass and formula for
a compound:
1. A compound is vaporized and then ionized.
2. The masses of the ions are detected and
graphed.

Sons, Inc.
15-44

Spectrometry
How does the mass of the radical cation
compare to the original molecule?
If the radical cation remains intact, it is known

as the molecular ion (M+) or parent ion.
Often, the molecular ion undergoes some
type of fragmentation.
Sons, Inc.
15-45

Spectrometry
The resulting fragments may undergo even
further fragmentation.
The ions are deflected by a magnetic field.

Smaller mass and higher charge fragments
as affected more by the magnetic field.
Neutral fragments are not detected.
Sons, Inc.
15-46
particles with different mass to charge ratios (m/z)
Chapter 15/48
Mass spectrometry:
http://www.youtube.com/watch?v=J-wao0O0_qM
Chapter 10/49

Spectrometry
MASS SPECTRUM
Relative Abundance
m/z values
base peak: tallest peak in
spectrum
Parent peak (M+).
Sometimes, the M+ peak is not
even observed in the spectrum
Sons, Inc.
15-50

Spectrometry
Peaks with a mass of less than M+ represent
fragments:
Subsequent H radicals can be fragmented to

give the ions with a mass/charge = 12, 13
and 14.
Sons, Inc.
15-51

Spectrometry
MS is a relatively sensitive analytical method.
Many organic compounds can be identified:
Pharmaceutical: drug discovery and drug metabolism,
reaction monitoring
Biotech: amino acid sequencing, analysis of
macromolecules
Clinical: neonatal screening, hemoglobin analysis
Environmental: drug testing, water quality, food
contamination testing
Geological: evaluating oil composition
Forensic: explosives detection
Many More
Sons, Inc.
15-52
15.9 Analyzing the M+ Peak

Mass spectrum for benzene (C6H6)

Sons, Inc.
15-53

Like most compounds, the M+ peak for
pentane is NOT the base peak.
The M+ peak fragments easily.

Sons, Inc.
15-54

First step: identify the M+ peak:
It will tell you the molar mass of the compound.
An odd massed M+ peak MAY indicate an odd
number of N atoms in the molecule.
An even massed M+ peak MAY indicate an even
number of N atoms or zero N atoms in the molecule.

Sons, Inc.
15-55
15.10 Analyzing the (M+1)+

Peak
Recall: (M+1)+ peak in

methane is about 1% as
abundant as the M+ peak.
(M+1)+ peak results from
the presence of 13C in the
sample.

Sons, Inc.
15-56

Peak
C isotope has the abundance of
13
1% of total
In decane (C10H22)
Molecules made of exclusively 12C
atoms
Molecules have at least one 13C
Natural abundance of deuterium is
0.015%. (1:10000)

Sons, Inc.
15-57

Peak isotopes:
Chlorine has two abundant
35
Cl=76% and
37
Cl=24%
Molecules with chlorine often have strong

(M+2)+ peaks.

Sons, Inc.
15-58

Peak
Br=51% and 81Br=49%, so molecules with

bromine often have equally strong (M)+ and
(M+2)+ peaks.
79

Sons, Inc.
15-59
Table 15-3, p. 620
15.12 Analyzing the

Fragments
A thorough analysis of the molecular fragments can often yield structural information.
pentane.
Remember, MS only detects charged fragments.

Sons, Inc.
15-61
15.12 Analyzing the

Fragments
N-Pentane mass spectrum

Sons, Inc.
15-62
Alkane Fragmentation Pattern
p. 626
Fig. 15-9, p. 627
15.12 Analyzing the

Fragments
Alcohols fragmentation:
alpha cleavage
dehydration.

Sons, Inc.
15-65
Alcohol Cleavage
Chapter 15/66
Fig. 15-12, p. 630
15.12 Analyzing the

Fragments
Amines fragmentation: alpha cleavage:
Carbonyls fragmentation: McLafferty

rearrangement:

Sons, Inc.
15-68
Aldehydes and Ketones Cleavage
Chapter 15/69
Fig. 15-13, p. 631
Chapter 10/71
Consider all possible fragments
Chapter 10/72
15.14 GC-Mass Spectrometry

MS is suited for the identification of pure
substances.
However, MS instruments are often
connected to a gas chromatograph (GC) so
mixtures can be analyzed.

Sons, Inc.
15-73
15.14 GC-Mass Spectrometry

GC-MS gives two main
forms of information:
1. The chromatogram
gives the retention time.
2. The Mass Spectrogram
(low-res or high-res).
GC-MS is a great
technique for detecting
compounds such as
drugs in solutions such
as blood or urine.
Sons, Inc.
15-74
Suggested Problems
Chapter &
Sections
15: 1-12
Problems - Excellent/Essential
15: 38-44,
Problems - Good
15: 55, 57, 59
Chapter 13/75

CHY242 Chapter 15 W16

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

CHY242 Chapter 15 W16

Enviado por

Direitos autorais:

Formatos disponíveis

CHY242

15.1 Introduction to Spectroscopy

15.1 Introduction to Spectroscopy

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

This chapter focuses on IR spectroscopy.

Klein, Organic Chemistry 1e

Interaction Electromagnetic Radiation

Interaction Electromagnetic Radiation

Wavenumber is the reciprocal of wavelength

Fig. 13-3, p. 505

Vibration in Organic Molecules

2012 Pearson Education, Inc.

This chapter will focus mostly

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

The region below 1500 cm -1 is called the

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Are the differences due to mass or bond

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

What if we have conjugation?

Klein, Organic Chemistry 1e

15.3 IR Signal Wavenumber

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.4 IR Signal Strength

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.4 IR Signal Strength

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

15.5 IR Signal Shape

OH stretching signals are often quite broad.

Klein, Organic Chemistry 1e

15.5 IR Signal Shape

Copyright 2012 John Wiley &