13 Lecture MS IR UV

Chapter 13
Mass
Spectrometry;
Infrared
Spectroscopy;
Ultraviolet/Visible
Spectroscopy
Paula Yurkanis Bruice

University of California,
Santa Barbara
© 2017 Pearson Education, Inc.
Instrumental Techniques
mass spectrometry
allows us to determine molecular mass and the molecular formula
infrared (IR) spectroscopy

allows us to identify the functional groups
ultraviolet/visible (UV/Vis) spectroscopy

provides information about compounds with conjugated
double bonds
nuclear magnetic resonance (NMR) spectroscopy

provides information about the carbon–carbon and
carbon–hydrogen framework

Classes of Organic Compounds

Mass Spectrometry
An electron is ejected from the compound,

thereby forming a molecular ion.

A Mass Spectrometer
Only positively charged species reach the recorder.

The Mass Spectrum of Pentane
m/z is the mass-to-charge ratio of the fragment because z = 1

The Molecular Ion
Pentane forms a molecular ion with m/z = 72.

Fragmentation of the Molecular Ion
The more stable the fragments, the more abundant they will be.
C-2–C-3 fragmentation forms more stable fragments.

The Peak at m/z = 57 is
More Abundant for Isopentane
Isopentane is more likely to lose a methyl group

because it forms a secondary carbocation.

More Stable Fragments are More Abundant
The peak at m/z = 57 is more abundant for

isopentane than for pentane because
a secondary carbocation is more stable than a primary carbocation.
Loss of H2 From a Carbocation
A peak at m/z value two units below the m/z value of the
carbocation is commonly observed.

The Natural Abundance of Isotopes

High Resolution Mass Spectrometry Can Distinguish
Between Compounds with the Same Molecular Mass
exact masses of isotopes
exact molecular masses

The Carbon–Bromine Bond
Breaks Heterolytically

The Carbon–Chlorine Bond Breaks Heterolytically;
The Carbon–Carbon Bond Breaks Homolytically
Bonds between atoms of different electronegativities break heterolytically.
Bonds between atoms of similar electronegativities break homolytically.

α-Cleavage in an Alkyl Chloride
The bonds that break are

the weakest bonds and
the bonds that form the most stable fragments.
Homolytic cleavage of the carbon–carbon bond

is called α-cleavage.

The Mass Spectrum of 2-Chloropentane

α-Cleavage Occurs in Alkyl Chlorides
but is Less Likely to Occur in Alkyl Bromides
Bond Dissociation Energy

C–Br = 71 kcal/mol
C–Cl = 85 kcal/mol
C–C = 89 kcal/mol
C–H = 99 kcal/mol
The carbon–carbon bond and the carbon–chlorine bond

have similar strengths.
The carbon–carbon bond is much stronger than the carbon–bromine bond.

Ethers
The fragmentation pattern of an ether

is similar to that of an alkyl halide.
The Carbon–Oxygen Bond
Breaks Heterolytically


The Carbon–Carbon Bond Breaks
Homolytically (α-Cleavage)

α-Cleavage in an Alcohol

Loss of a Water from an Alcohol
The molecular ion of an alcohol is often not seen because if it

has a hydrogen on a γ-carbon, it readily loses water.
In this fragmentation, two bonds are broken.

α-Cleavage in a Ketone

Loss of a Hydrogen from a γ-Carbon
In this fragmentation, two bonds are broken.

Common Fragmentation Behavior of Alkyl
Halides, Ethers, Alcohols, and Ketones
1. A bond between carbon and a more electronegative atom

breaks heterolytically.
2. A bond between carbon and an atom of similar

electronegativity breaks homolytically.
3. The bonds most likely to break are the weakest bonds and
those that lead to formation of the most stable cation.

Gas Chromatography-Mass
Spectrometry
1. Mixtures of compounds can be analyzed using gas

chromatography and mass spectrometry (GC-MS) at the
same time.
2. The sample is injected into a gas chromatograph, and the

various components of the mixture travel through the
column at different rates, based on their boiling points.
3. The mass spectrometer records the mass spectrum for

each component of the mixture.

The Electromagnetic Spectrum
high energy low energy

The Greater the Energy, the Greater the Frequency
The Greater the Energy, the Shorter the Wavelength

Wavelength
wave number = the number of waves in 1 cm

A Stretching Vibration
(two atoms)
A stretching vibration occurs along the line of the bond.

Stretching and Bending Vibrations
(three or more Atoms)

Each Stretching and Bending Vibration
Occurs at a Characteristic Wavenumber

The Functional Group Region (4000–1400 cm−1)
The Fingerprint Region (1400–600 cm−1)
Functional group regions: Fingerprint regions:

Both compounds are alcohols. Compounds are different alcohols.

IR Stretching Frequencies

The More Polar the Bond,
the More Intense the Absorption
The greater the change in dipole moment,

the more intense the absorption.

Hooke’s Law
Lighter atoms show absorption

bands at larger wavenumbers.
C―H ~3000 cm−1
C―D ~2200 cm−1
C―O ~1100 cm−1
C―Cl ~ 700 cm−1

The Greater the Bond Order,
the Larger the Wavenumber

Electron Delocalization (Resonance)
Affects the Frequency of the Absorption
The more double bond character,

the greater the frequency (wavenumber).

This C═O Bond is Essentially a
Pure Double Bond
pure double bond 1720 cm−1

This C═O Bond Has Significant
Single-Bond Character
double bond with some single-bond character 1680 cm−1
The less double-bond character, the lower the frequency.

Resonance Electron Donation Decreases the Frequency
Inductive Electron Withdrawal Increases the Frequency

The IR Spectrum of an Ester
carbonyl group 1740 cm−1

The IR Spectrum of an Amide
carbonyl group 1660 cm−1

Carbon–Oxygen Bonds
The carbon–oxygen bond in an alcohol is a pure single bond.
The carbon–oxygen bond in an ether is a pure single bond.
The carbon–oxygen bond in a carboxylic acid has partial

double-bond character.
One carbon–oxygen single bond in an ester is a pure single bond,

and one has partial double-bond character.

Hydrogen-Bonded OH Groups are Broad
and Stretch at a Lower Frequency
It is easier to stretch a hydrogen-bonded OH group.

The IR Spectrum of an Alcohol
broad O—H stretch

The IR Spectrum of a Carboxylic Acid
broader O—H stretch

Carbon–Hydrogen Stretching Vibrations

The Strength of a Carbon–Hydrogen Bond
Depends on the Hybridization of the Carbon
An sp3-carbon–hydrogen bond is the weakest,

so its stretch occurs at the shortest wavenumber (< 3000 cm−1).

Where Carbon–Hydrogen Bonds
Stretch and Bend
Stretching vibrations require more energy than bending vibrations.
An sp3-carbon–hydrogen stretch occurs at < 3000 cm−1.

An sp2-carbon–hydrogen stretch occurs at > 3000 cm−1.
Where Carbon–Hydrogen Bonds Bend
An sp3-carbon–hydrogen bend of a methyl occurs at < 1400 cm−1.
An sp2-carbon–hydrogen bend of a methyl and/or a methylene

occurs at > 1400 cm−1.
The IR Spectrum of an Aldehyde
The carbon–hydrogen stretch of an aldehyde hydrogen occurs

at 2820 cm−1 and at 2720 cm−1.

Carbon–Hydrogen Bending Vibrations

The IR Spectrum of an Amine
N—H bend 1600 cm−1

The IR Spectrum of Diethyl Ether
The absence of absorption bands can help identify spectra.

Some Vibrations are Infrared Inactive
A bond absorbs IR radiation

only if its dipole moment changes when it vibrates.

The IR Spectrum of 2-Methyl-1-Pentene
Wavenumber (cm−1) Assignment
3075 sp2 CH
2950 sp3 CH
1650 and 890 terminal alkene with two substituents
absence of bands
1500–1430 and 720 fewer than four adjacent CH2 groups
The IR Spectrum of Benzaldehyde
3050 sp2 CH
2810 and 2730 aldehyde
1600 and 1460 benzene ring
1700 partial single-bond character carbonyl

The IR Spectrum of 2-Propyn-1-ol
3300 OH group
2950 sp3 CH
2100 alkyne

The IR Spectrum of N-Methylethanamide
3300 N—H
2950 sp3 CH
1660 amide carbonyl
1560 N—H bend

IR Spectrum of Ethyl Benzyl Ketone
> 3000 sp2 CH

< 3000 sp3 CH
1605 and 1500 benzene ring
1720 ketone carbonyl
1380 methyl group
Ultraviolet and Visible Spectroscopy
UV/Vis spectroscopy provides information

about compounds with
conjugated double bonds.

An Electronic Transition
Only organic compounds with π electrons

can produce UV/Vis spectra.
A UV spectrum is obtained when

UV light (180 to 400 nm) is absorbed.
A visible spectrum is obtained when

visible light (400 to 780 nm) is absorbed.
A UV Spectrum

UV/Vis Absorption Bands are Broad
UV/Vis absorption bands are broad

because an electronic state has vibrational sublevels.

Chromophore
All these compounds have the same UV spectrum.
A chromophore is that part of a molecule that is responsible

for a UV/Vis spectrum.

The Beer–Lambert Law
A=εcl
A = absorbance of the sample
c = concentration of substance in solution
l = length of the light path in cm
ε = molar absorptivity of the sample

(characteristic of the compound)

Cells Used for Taking UV/Vis Spectra

The More Conjugated Double Bonds,
the Longer the Wavelength

The More Conjugated Double Bonds,
the Longer the Wavelength

Conjugation Makes the
Electronic Transition Easier

Colored Compounds Absorb
Visible Light (> 400 nm)
β-Carotene is found in carrots, apricots, and flamingo feathers.
Lycopene is found in tomatoes, watermelon, and pink grapefruit.

Auxochrome
An auxochrome is a substituent that

alters the position and intensity of the absorption.

Common Dyes

Anthocyanins
Responsible for the red, purple, and blue colors

of many flowers and fruits.

UV/Vis Spectroscopy Can Be Used
to Measure the Rate of a Reaction

to Measure the Rate of a Reaction

to Determine a pKa Value
The phenolate ion absorbs at 287 nm, but phenol does not.
to Determine the Melting Temperature of DNA
The temperature increases with

increasing numbers of G-C base pairs.

13 Lecture MS IR UV

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Chapter 13

Paula Yurkanis Bruice

infrared (IR) spectroscopy

ultraviolet/visible (UV/Vis) spectroscopy

nuclear magnetic resonance (NMR) spectroscopy

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

An electron is ejected from the compound,

© 2017 Pearson Education, Inc.

Only positively charged species reach the recorder.

m/z is the mass-to-charge ratio of the fragment because z = 1

© 2017 Pearson Education, Inc.

Pentane forms a molecular ion with m/z = 72.

© 2017 Pearson Education, Inc.

C-2–C-3 fragmentation forms more stable fragments.

Isopentane is more likely to lose a methyl group

© 2017 Pearson Education, Inc.

The peak at m/z = 57 is more abundant for

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

exact masses of isotopes

exact molecular masses

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

Bonds between atoms of different electronegativities break heterolytically.

Bonds between atoms of similar electronegativities break homolytically.

The bonds that break are

Homolytic cleavage of the carbon–carbon bond

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

Bond Dissociation Energy

The carbon–carbon bond and the carbon–chlorine bond

The carbon–carbon bond is much stronger than the carbon–bromine bond.

© 2017 Pearson Education, Inc.

The fragmentation pattern of an ether

The fragmentation pattern of an ether

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

The molecular ion of an alcohol is often not seen because if it

In this fragmentation, two bonds are broken.

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

In this fragmentation, two bonds are broken.

© 2017 Pearson Education, Inc.

1. A bond between carbon and a more electronegative atom

2. A bond between carbon and an atom of similar

© 2017 Pearson Education, Inc.

1. Mixtures of compounds can be analyzed using gas

2. The sample is injected into a gas chromatograph, and the

3. The mass spectrometer records the mass spectrum for

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

wave number = the number of waves in 1 cm

© 2017 Pearson Education, Inc.

A stretching vibration occurs along the line of the bond.

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

Functional group regions: Fingerprint regions:

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.