Spectroscopies

SPECTROSCOPY
IR spectroscopy, UV-
UV-Visible spectroscopy,
Mass Spectrometry, NMR spectroscopy
13- 1
Principles of Molecular Spectroscopy
Spectroscopy::
Electromagnetic Radiation
13- 2
Definitions
• Spectroscopy-
Spectroscopy- the study of the light from an object.
• Spectrometer
Spectrometer-- an instrument which spreads out light
making a spectra.
• Spectra
Spectra-- range of electromagnetic energy separated
by wavelength.
Electromagnetic Radiation
is propagated at the speed of light
has properties of particles and waves

the energy of a photon is proportional
to its frequency
13- 4
Figure 1: The Electromagnetic Spectrum
Shorter Wavelength () Longer Wavelength ()
400 nm 750 nm
Visible Light
Higher Frequency () Lower Frequency ()
Higher Energy (E) Lower Energy (E)
13- 5
Figure 2. The Electromagnetic Spectrum
Shorter Wavelength (
() Longer Wavelength (
( )
Ultraviolet Infrared
Higher Frequency (
() Lower Frequency (
()
Higher Energy (E) Lower Energy (E)
13- 6
Figure 3. The Electromagnetic Spectrum
Cosmic rays
 Rays
X-rays
Energy Ultraviolet light
Visible light
Infrared radiation
Microwaves
Radio waves
13- 7
2 Basic Types of Spectra
• Continuous-
Continuous- energy of all wavelengths
• Discrete
Discrete-- energy at a particular wavelength
– Emission or bright lines
– Absorption or dark lines
Continuous Spectrum
• Also called thermal

or blackbody
spectra
• Spectra of stars,
planets, moons
• Depends on
temperature
Ex: sunlight passing
through a prism
Continuous Spectrum continued
Hotter objects
Shift toward this end
Longer
wavelengt
h
Shorter
wavelength
Cooler objects
Shift toward this end
Discrete Spectrum
Absorption
Each
element has
a unique
Ex: stars, signature of
planets w/ absorption
atmospher lines. That
es, & pattern
galaxies helps
scientists
Spectra Cool, identify the
Absorption
thin element(s).
gas spectrum
Hot object
Discreet spectrum-
spectrum- Again, the
Emission pattern of
the lines
determines
the identity
of the
element.
Ex: comets, nebula

& certain stars
Cold, Thin, hot

empty Emission
gas spectrum
space
Spectra
Ex: comets, nebula
& certain stars
Cold, Thin,
empty Emission
hot gas spectrum
space
Spectra
Ex: stars,
planets w/
atmospheres,
& galaxies
Spectra
Cool, thin gas Absorption
spectrum
Hot object
Motion of Objects in Space
Compare the dark lines in the middle spectra to

the dark lines in the other two spectra. Blue shift shows object is
moving toward the observer.
This shows the

normal position
or no motion.
This shows a red
shift meaning that
the object is moving
away from the
observer.
Principles of Molecular Spectroscopy:
Quantized Energy States
13- 15
E = h
h
Electromagnetic radiation is absorbed when the

energy of photon corresponds to difference in
energy between two states.
13- 16
What Kind of States?
electronic UV--Vis
UV
vibrational infrared
rotational microwave
nuclear spin radiofrequency
13- 17
Infrared Spectroscopy
Gives information about the functional groups

in a molecule
13- 18
Infrared Spectroscopy
region of infrared that is most useful lies between

2.5--16 m (4000-
2.5 (4000-625 cm-1)
depends on transitions between vibrational

energy states
stretching
bending
13- 19
Stretching Vibrations of a CH2 Group
Symmetric Antisymmetric
13- 20
Bending Vibrations of a CH2 Group
In plane In plane
13- 21
Bending Vibrations of a CH2 Group
Out of plane Out of plane
13- 22
Figure 4. Infrared Spectrum of Hexane
bending
C—H stretching
bending bending
CH3CH2CH2CH2CH2CH3
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fifth Edition. Copyright © 2003 The McGraw-Hill Companies, Inc. All rights reserved.
13- 23
Figure 5. Infrared Spectrum of 1-
1-Hexene
C=C
C=C—
C=C —H H —C
H2C=C
H2C=CHCH2CH2CH2CH3
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
13- 24
Infrared Absorption Frequencies
Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
sp C—H 3310--3320
3310
sp2 C—H 3000--3100
3000
sp3 C—H 2850--2950
2850
sp2 C—O 1200
sp3 C—O 1025--1200
1025
13- 25

Stretching vibrations (multiple bonds)
C C 1620--1680
1620
—C C— 2100--2200
2100
—C N 2240--2280
2240
13- 26
Structural unit Frequency, cm-1 C O

Stretching vibrations (carbonyl groups)
Aldehydes and ketones 1710--1750
1710
Carboxylic acids 1700--1725
1700
Acid anhydrides 1800--1850 and 1740-
1800 1740-1790
Esters 1730--1750
1730
Amides 1680--1700
1680
13- 27

Bending vibrations of alkenes
RCH CH2 910--990

910
R2C CH2 890
cis--RCH
cis CHR' 665--730
665
trans--RCH
trans CHR' 960--980
960
R2C CHR' 790--840

790
13- 28

Bending vibrations of derivatives of benzene
Monosubstituted 730--770 and 690-
730 690-710
Ortho--disubstituted
Ortho 735--770
735
Meta--disubstituted
Meta 750--810 and 680-
750 680-730
Para--disubstituted
Para 790--840
790
13- 29
Figure 6. Infrared Spectrum of tert
tert--butylbenzene
Ar—
Ar —H
H H
H H C6H5C(CH3)3
C C
H H C H
C H
H H H
H
H —C Monsubstituted
H
H benzene
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
13- 30

Stretching vibrations (single bonds)
O—H (alcohols) 3200--3600
3200
O—H (carboxylic acids) 3000--3100
3000
N—H 3350--3500
3350
13- 31
2-Hexanol
H —C
O —H
CH3CH2CH2CH2CHCH3
OH
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
13- 32
2-Hexanone
CH3CH2CH2CH2CCH3
O
H—C
C=O
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
13- 33
Advantages
• Provide the fingerprint for the sample being

analyzed
• The installation of instrument to the computer
allows the comparison of sample spectrum
and standard reference can be run
simultaneously
Disadvantages
• Rarely used for quantitative purpose since the

spectrum produced is too complicated to
determine one by one
• The sample preparation is quite difficult,
needs the skill to handle it.
Ultraviolet--Visible (UV-
Ultraviolet (UV-VIS) Spectroscopy
Gives information about conjugated  electron

systems
13- 36
Transitions between electron energy states
gaps between electron energy

levels are greater than those
between vibrational levels
 E = h
gap corresponds to wavelengths
between 200 and 800 nm
13- 37
Conventions in UV-
UV-VIS
X-axis is wavelength in nm (high energy at left,

low energy at right)
max is the wavelength of maximum absorption
and is related to electronic makeup of molecule
molecule--
especially  electron system
Y axis is a measure of absorption of electromagnetic
radiation expressed as molar absorptivity ()
13- 38
UV Spectrum of cis,trans-
cis,trans-1,3
1,3--cyclooctadiene
2000
Molar max 230 nm
( )
absorptivity (
max 2630
1000
200 220 240 260 280
Wavelength, nm
13- 39
** Transition in cis,trans-
 cis,trans-1,3
1,3--cyclooctadiene
  
LUMO   
 E = h
HOMO  
 
Most stable
-electron -Electron
configuration configuration of
excited state
Highest occupied molecular orbital (HOMO) to the lowest unoccupied
molecular orbital (LUMO), and the resulting species is called an excited state. 13- 40
** Transition in Alkenes

HOMO-LUMO energy gap is affected by

HOMO-
substituents on double bond
as HOMO-
HOMO-LUMO energy difference
decreases (smaller E), max shifts to longer
wavelengths
13- 41
Methyl groups on double bond cause max
to shift to longer wavelengths
H H H CH3
C C C C
H H H CH3
max 170 nm max 188 nm
13- 42
Extending conjugation has a larger effect
on max; shift is again to longer
wavelengths
H H H H
C C C C H
H H H C C
H H
max 170 nm
max 217 nm
13- 43
H H
C C H
H max 217 nm
C C
(conjugated diene
diene))
H H
H3C H
C C H max 263 nm
H C C H conjugated triene plus
two methyl groups
H C C
H CH3
13- 44
Lycopene
orange--red pigment in tomatoes

orange
max 505 nm
13- 45
Mass Spectrometry
13- 46
Principles of Electron-
Electron-Impact Mass Spectrometry
Atom or molecule is hit by high-

high-energy electron
e–
13- 47

e–
electron is deflected but transfers much of its

energy to the molecule
13- 48

e–
electron is deflected but transfers much of its

energy to the molecule
13- 49
This energy-
energy-rich species ejects an electron.
13- 50
This energy-
energy-rich species ejects an electron.
+ e–
•
forming a positively charged, odd-

odd-electron species
called the molecular ion
13- 51
Molecular ion passes between poles of a

magnet and is deflected by magnetic field
amount of
deflection depends
on mass-
mass-to
to--charge
ratio
+
highest m/z •
deflected least
lowest m/z
deflected most
13- 52
If the only ion that is present is the molecular ion,

mass spectrometry provides a way to measure the
molecular weight of a compound and is often used for
this purpose.
However, the molecular ion often fragments to a
mixture of species of lower m/z.
13- 53
The molecular ion dissociates to a cation

and a radical.
+
•
13- 54
The molecular ion dissociates to a cation

and a radical.
+ •
Usually several fragmentation pathways are available

and a mixture of ions is produced.
13- 55
mixture of ions of
different mass
gives separate peak
for each m/z
intensity of peak
proportional to
percentage of each + +
ion of different
mass in mixture + +
+
separation of peaks
depends on relative
+
mass
13- 56
mixture of ions of
different mass
gives separate peak
for each m/z
intensity of peak + + + +
proportional to
percentage of each + +
atom of different
mass in mixture
separation of peaks
depends on relative
mass
13- 57
Some molecules undergo very little fragmentation
Benzene is an example. The major peak

corresponds to the molecular ion.
Relative
intensity
100
80 m/z = 78
60
40
20
0
20 40 60 80 100 120
m/z
13- 58
Isotopic Clusters
H H H
H H H H H H
78 79 79
H H H H H H
H H H
93.4% 6.5% 0.1%

all H are one C is 13C one H is 2H
1H and all
C are 12C 13- 59

Isotopic Clusters 35Cl 37Cl
in Chlorobenzene
Relative visible in peaks for

intensity molecular ion
100
80 112
60
40 114
m/z
20
0 20 40 60 80 100 120
13- 60
Isotopic Clusters +
H H
in Chlorobenzene
Relative no m/z 77, 79 pair; H H

intensity therefore ion
responsible for H
m/z 77 peak does
100
not contain Cl
80
60 77
40 m/z
20
0 20 40 60 80 100 120
13- 61
Alkanes undergo extensive fragmentation
CH3—CH2—CH2—CH2—CH2—CH2—CH2—CH2—CH2—CH3
Relative 43
intensity
57
100
80 Decane
60
71
40
85
20 99 142
0 20 40 60 80 100 120
m/z
13- 62
Propylbenzene fragments mostly
at the benzylic position
Relative
intensity
100
91
80
CH2—CH2CH3
60
40
120
20
0 20 40 60 80 100 120
m/z
13- 63
Molecular Formula
as a
Clue to Structure
13- 64
Molecular Weights
One of the first pieces of information we try to

obtain when determining a molecular
structure is the molecular formula.
However, we can gain some information even
from the molecular weight. Mass
spectrometry makes it relatively easy to
determine molecular weights.
13- 65
The Nitrogen Rule
A molecule with an
odd number of NH2 93
nitrogens has an odd
molecular weight.
A molecule that O2N NH2 138
contains only C, H,
and O or which has
an even number of NO2
nitrogens has an
even molecular O2N NH2 183
weight.
13- 66
Exact Molecular Weights
CH3(CH2)5CH3 CH3CO
Heptane Cyclopropyl acetate
Molecular formula C7H16 C5H8O2

Molecular weight 100 100
Exact mass 100.1253 100.0524

Mass spectrometry can measure exact
masses. Therefore, mass spectrometry can
give molecular formulas.
13- 67
Molecular Formulas
Knowing that the molecular formula of a

substance is C7H16 tells us immediately that is
an alkane because it corresponds to CnH2n+2
C7H14 lacks two hydrogens of an alkane,
therefore contains either a ring or a double
bond
13- 68
Index of Hydrogen Deficiency
relates molecular formulas to multiple bonds

and rings
index of hydrogen deficiency =
1 (molecular formula of alkane –

2 molecular formula of compound)
13- 69
Example 1
C7H14
index of hydrogen deficiency
= 1 (molecular formula of alkane –

2
molecular formula of compound)
= 1 (C7H16 – C7H14)
2
= 1 (2) = 1
2
Therefore, one ring or one double bond.
13- 70
Example 2
C7H12
= 1 (C7H16 – C7H12)
2
= 1 (4) = 2
2
Therefore, two rings, one triple bond,

two double bonds, or one double bond + one ring.
13- 71
Oxygen has no effect
CH3(CH2)5CH2OH (1-
(1-heptanol, C7H16O) has
same number of H atoms as heptane
1 (C7H16 – C7H16O) = 0
2
no rings or double bonds
13- 72
Oxygen has no effect
CH3CO
Cyclopropyl acetate
1 (C H – C H O ) = 2
5 12 5 8 2
2
one ring plus one double bond
13- 73
If halogen is present
Treat a halogen as if it were hydrogen.
H Cl
C3H5Cl
C C
same index of hydrogen
H CH3
deficiency as for C3H6
13- 74
Rings versus Multiple Bonds
Index of hydrogen deficiency tells us the sum of

rings plus multiple bonds.
Catalytic hydrogenation tells us how many

multiple bonds there are.
13- 75
Introduction to
1H NMR Spectroscopy
13- 76
The nuclei that are most useful to
organic chemists are:
1H and 13C
both have spin = ±1/2
1H is 99% at natural abundance
13C is 1.1% at natural abundance
13- 77
Nuclear Spin
+ +
A spinning charge, such as the nucleus of 1H

or 13C, generates a magnetic field.
field. The
magnetic field generated by a nucleus of spin
+1/2 is opposite in direction from that
generated by a nucleus of spin –1/2.
13- 78
The distribution of
nuclear spins is +
random in the
absence of an
external magnetic
field. +
+
+
13- 79
An external magnetic
field causes nuclear +
magnetic moments to
align parallel and
antiparallel to applied
field. +
+
H0
+
+
13- 80
There is a slight
excess of nuclear +
magnetic moments
aligned parallel to
the applied field.
+
+
H0
+
+
13- 81
Energy Differences Between Nuclear Spin States
E E '
increasing field strength
no difference in absence of magnetic field

proportional to strength of external magnetic field
13- 82
Some important relationships in NMR
Units
The frequency of absorbed
electromagnetic radiation Hz
is proportional to
the energy difference between

kJ/mol
two nuclear spin states
(kcal/mol)
which is proportional to
the applied magnetic field tesla (T)

13- 83
The frequency of absorbed electromagnetic

radiation is different for different elements,
and for different isotopes of the same element.
For a field strength of 4.7 T:

1H absorbs radiation having a frequency
of 200 MHz (200 x 106 s-1)

13C absorbs radiation having a frequency
of 50.4 MHz (50.4 x 106 s-1)

13- 84
The frequency of absorbed electromagnetic

radiation for a particular nucleus (such as 1H)
depends on its molecular environment.
This is why NMR is such a useful tool

for structure determination.
13- 85
Nuclear Shielding
and
1H Chemical Shifts
What do we mean by "shielding?"

What do we mean by "chemical shift?"
13- 86
Shielding
An external magnetic field

affects the motion of the
electrons in a molecule,
inducing a magnetic field
C H
within the molecule.
The direction of the
induced magnetic field is
opposite to that of the
applied field. H0
13- 87
Shielding
The induced field shields

the nuclei (in this case, C
and H) from the applied
field.
C H
A stronger external field is
needed in order for energy
difference between spin
states to match energy of
rf radiation. H0
13- 88
Chemical Shift
Chemical shift is a
measure of the degree to
which a nucleus in a
molecule is shielded.
C H
Protons in different
environments are shielded
to greater or lesser
degrees; they have
different chemical shifts. H0
13- 89
Chemical Shift
(δ) are
Chemical shifts (δ CH3
measured relative to the
protons in H3C Si CH3
tetramethylsilane (TMS)
as a standard.
CH3
position of signal - position of TMS peak

δ = x 106
spectrometer frequency
13- 90
Downfield Upfield
Decreased shielding Increased shielding
(CH3)4Si (TMS)
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
Chemical shift (
(, ppm)
measured relative to TMS
13- 91
Chemical Shift
Example: The signal for the proton in chloroform

(HCCl3) appears 1456 Hz downfield from TMS at a
spectrometer frequency of 200 MHz.
position of signal - position of TMS peak

= x 106
spectrometer frequency
1456 Hz - 0 Hz
= x 106
200 x 106 Hx
= 7.28
13- 92
Cl
 7.28 ppm
H C Cl
Cl
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
(, ppm)
Chemical shift (
13- 93
Effects of Molecular Structure
on
1H Chemical Shifts
protons in different environments experience

different degrees of shielding and have
different chemical shifts
13- 94
Electronegative substituents decrease
the shielding of methyl groups
least shielded H most shielded H
CH3F CH3OCH3 (CH3)3N CH3CH3 (CH3)4Si
4.3 3.2 2.2 0.9 0.0
13- 95
Electronegative substituents decrease shielding
δ 0.9 δ 1.3 δ 0.9

H3C—CH2—CH3
δ 4.3 δ 2.0 δ 1.0

O2N—CH2—CH2—CH3
13- 96
Effect is cumulative
CHCl3
CHCl  7.3
CH2Cl2  5.3
CH3Cl  3.1
13- 97
Methyl, Methylene, and Methine
CH3 more shielded than CH2 ;

CH2 more shielded than CH
CH
δ 0.9 δ 0.9
CH3 CH3
δ 1.2 δ 0.8
H3C C H δ 1.6 H3C C CH2 CH3
CH3 CH3
13- 98
Protons attached to sp2 hybridized carbon
are less shielded than those attached
to sp3 hybridized carbon
H
H H H H
C C CH3CH3
H H H H
H
 7.3  5.3  0.9
13- 99
But protons attached to sp hybridized carbon
are more shielded than those attached
to sp2 hybridized carbon
 5.3
H H
 2.4
C C H C C CH2OCH3
H H
13- 100
Protons attached to benzylic and allylic
carbons are somewhat less shielded than usual
H3C CH3
 1.5  0.8
δ 0.9 δ 1.3 δ 0.9

H3C—CH2—CH3
 1.2  2.6
H3C CH2
13- 101
Proton attached to C=O of aldehyde
is most deshielded C—
C—H
δ 2.4
H O
H3C C C H δ 9.7
CH3
δ 1.1
13- 102
Type of proton Chemical shift (
(), Type of proton Chemical shift (
(),
ppm ppm
H C R 0.9--1.8
0.9 H C C N 2.1--2.3
2.1
H C C C 1.5
1.5--2.6 H C C C 2.5
H C C 2.0--2.5
2.0 H C Ar 2.3--2.8
2.3
13- 103
(), Type of proton Chemical shift (
(),
ppm ppm
H C NR 2.2--2.9
2.2
H
C C 4.5--6.5
4.5
H C Cl 3.1--4.1
3.1
H Ar 6.5--8.5
6.5
H C Br 2.7--4.1
2.7
O
3.3--3.7
3.3 H C 9-10
H C O
13- 104
(),
ppm
H NR 1-3
H OR 0.5--5
0.5
H OAr 6-8
HO C 10--13
10
13- 105
Interpreting Proton NMR
Spectra
13- 106
Information contained in an NMR
spectrum includes:
1. number of signals
2. their intensity (as measured by area

under peak)
3. splitting pattern (multiplicity)
13- 107
Number of Signals
protons that have different chemical shifts

are chemically nonequivalent
exist in different molecular environment
13- 108
N CCH
CCH2OC
OCH
H3
OCH
OCH3
NCCH
NCCH2O
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
(, ppm)
Chemical shift (
13- 109
Chemically equivalent protons
are in identical environments
have same chemical shift

replacement test: replacement by some
arbitrary "test group" generates same compound
H3CCH2CH3
chemically equivalent
13- 110
Chemically equivalent protons
Replacing protons at C-
C-1 and C-
C-3 gives same
compound (1-
(1-chloropropane)
C-1 and C-
C-3 protons are chemically
equivalent and have the same chemical shift
ClC
Cl CH2CH2CH3 CH3CH2CH2Cl
H3CCH2CH3
chemically equivalent
13- 111
Diastereotopic protons
replacement by some arbitrary test group

generates diastereomers
diastereotopic protons can have different
chemical shifts
Br H  5.3 ppm
C C
H3C H  5.5 ppm
13- 112
Spin--Spin Splitting
Spin
in
NMR Spectroscopy
not all peaks are singlets
signals can be split by coupling of

nuclear spins
13- 113
Figure 13.12 Cl2CHCH3
4 lines; 2 lines;
quartet doublet
CH CH3
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
(, ppm)
Chemical shift (
13- 114
Two--bond and three-
Two three-bond coupling
H
C C H C C H
H
protons separated by protons separated by
two bonds three bonds
(geminal relationship) (vicinal relationship)
13- 115
Two--bond and three-
Two three-bond coupling
H
C C H C C H
H
in order to observe splitting, protons cannot

have same chemical shift
coupling constant (2J or 3J) is independent

of field strength
13- 116
Figure 13.12 Cl2CHCH3
4 lines; 2 lines;
quartet doublet
CH CH3
10.0protons
coupled 9.0 8.0are7.0 6.0 (three-
vicinal 5.0 4.0
(three -bond 3.0 2.0 1.0 0
coupling)
CH splits CH
CH3 into Chemical (H, 3ppm)
a doublet,shiftCH
C( splits CH
CH into a quartet
Why do the methyl protons of
1,1--dichloroethane appear as a doublet?
1,1
Cl H
signal for methyl
H C C H protons is split into
a doublet
Cl H
To explain the splitting of the protons at C-

C-2,
we first focus on the two possible spin
orientations of the proton at C-
C-1
13- 118
1,1
Cl H
signal for methyl
a doublet
Cl H
There are two orientations of the nuclear spin

for the proton at C-
C-1. One orientation shields
the protons at C-
C-2; the other deshields the C-
C-
2 protons.
13- 119
1,1
Cl H
signal for methyl
a doublet
Cl H
The protons at C-
C-2 "feel" the effect of both the
applied magnetic field and the local field
resulting from the spin of the C-
C-1 proton.
13- 120
1,1
Cl H
"true" chemical
H C H shift of methyl
C
protons (no coupling)
Cl H
this line corresponds this line corresponds
to molecules in which to molecules in which
the nuclear spin of the nuclear spin of
the proton at C-
C -1 the proton at C-
C -1
reinforces opposes
the applied field the applied field
13- 121
Why does the methine proton of
1,1--dichloroethane appear as a quartet?
1,1
Cl H
signal for methine
proton is split into H C C H
a quartet
Cl H
The proton at C-
C-1 "feels" the effect of the
applied magnetic field and the local fields
resulting from the spin states of the three
methyl protons. The possible combinations
are shown on the next slide.
13- 122
Why does the methine proton of
1,1--dichloroethane appear as a quartet?
1,1
Cl H There are eight combinations of

nuclear spins for the three methyl
H C C H protons.
These 8 combinations split the
Cl H signal into a 1:3:3:1 quartet.
13- 123
The splitting rule for 1H NMR
For simple cases, the multiplicity of a signal

for a particular proton is equal to the number
of equivalent vicinal protons + 1.
13- 124
Splitting Patterns:
The Ethyl Group
CH3CH2X is characterized by a triplet-

triplet-quartet
pattern (quartet at lower field than the triplet)
13- 125
BrCH
BrC H2CH3
4 lines; 3 lines;
quartet triplet
CH3
CH2
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
(, ppm)
Chemical shift (
13- 126
Table 13.2
Splitting Patterns of Common Multiplets

Number of equivalent Appearance Intensities of lines
protons to which H of multiplet in multiplet
is coupled
1 Doublet 1:1
2 Triplet 1:2:1
3 Quartet 1:3:3:1
4 Pentet 1:4:6:4:1
5 Sextet 1:5:10:10:5:1
6 Septet 1:6:15:20:15:6:1
13- 127
Splitting Patterns:
The Isopropyl Group
(CH3)2CHX is characterized by a doublet-

doublet-
septet pattern (septet at lower field than the
doublet)
13- 128
BrCH
BrC H(C
(CH
H3)2
2 lines;
7 lines; doublet
septet
CH3
CH
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
(, ppm)
Chemical shift (
13- 129
13C NMR Spectroscopy
13- 130
1H and 13C NMR compared:
both give us information about the number of

chemically nonequivalent nuclei
(nonequivalent hydrogens or nonequivalent
carbons)
both give us information about the
environment of the nuclei (hybridization state,
attached atoms, etc.)
it is convenient to use FT-
FT-NMR techniques for
1H; it is standard practice for 13C NMR
13- 131
13C requires FT-

FT-NMR because the signal for a
carbon atom is 10-4 times weaker than the
signal for a hydrogen atom
a signal for a 13C nucleus is only about 1% as
intense as that for 1H because of the magnetic
properties of the nuclei, and
at the "natural abundance" level only 1.1% of all
the C atoms in a sample are 13C (most are 12C)
13- 132
13C signals are spread over a much wider

range than 1H signals making it easier to
identify and count individual nuclei
Figure 13.23 (a) shows the 1H NMR spectrum
of 1-
1-chloropentane; Figure 13.23 (b) shows
the 13C spectrum. It is much easier to identify
the compound as 1-1-chloropentane by its 13C
spectrum than by its 1H spectrum.
13- 133
1H
ClC
Cl CH2 CH3
ClC
Cl CH2CH2CH2CH2CH3
10.09.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

(, ppm)
Chemical shift (
13- 134
13C
ClCH
Cl CH2CH2CH2CH2CH3
a separate, distinct
peak appears for
each of the 5 carbons
CDCl3
200 180 160 140 120 100 80 60 40 20 0
(, ppm)
Chemical shift (
13- 135
13C Chemical Shifts
()
are measured in ppm (
from the carbons of TMS
13- 136
13C Chemical shifts are most affected by:
electronegativity of groups attached to carbon
hybridization state of carbon
13- 137
Electronegativity Effects
Electronegativity has an even greater effect

on 13C chemical shifts than it does on 1H
chemical shifts.
13- 138
Types of Carbons
Classification Chemical shift, δ

1H 13C
CH4 0.2 -2
CH3CH3 primary 0.9 8
CH3CH2CH3 secondary 1.3 16
(CH3)3CH tertiary 1.7 25
(CH3)4C quaternary 28
Replacing H by C (more electronegative) deshields
C to which it is attached.
13- 139
Electronegativity effects on CH3
Chemical shift, δ
1H 13C
CH4 0.2 -2
CH3NH2 2.5 27
CH3OH 3.4 50
CH3F 4.3 75
13- 140
Electronegativity effects and chain length
Cl CH2 CH2 CH2 CH2 CH3
Chemical 45 33 29 22 14
shift, δ
Deshielding effect of Cl decreases as

number of bonds between Cl and C increases.
13- 141
13C Chemical shifts are most affected by:
electronegativity of groups attached to carbon
hybridization state of carbon
13- 142
Hybridization effects
sp3 hybridized
carbon is more 36
114
shielded than sp2
138 36 126
126--142
sp hybridized
carbon is
more H C C CH2 CH2 CH3
shielded than 68 84 22 20 13
sp2, but less
shielded than
sp3
13- 143
Carbonyl carbons are especially deshielded
CH2 C O CH2 CH3

41 171 61 14
127--134
127
13- 144
Table 13.3
(), Type of carbon

Type of carbon Chemical shift ( (),
Chemical shift (
ppm ppm
RCH3 0-35 RC CR 65--90

65
R2CH2 15--40
15 R2C CR2 100--150
100
R3CH 25--50
25
110--175
110
R4C 30--40
30
13- 145
Table 13.3
(), Type of carbon

Type of carbon Chemical shift ( (),
Chemical shift (
ppm ppm
RCH2Br 20--40
20 RC N 110--125
110
O
RCH2Cl 25--50
25
RCOR 160--185
160
RCH2NH2 35--50
35
RCH2OH 50--65
50 O
RCH2OR 50--65
50 RCR 190--220
190
13- 146
13C NMR and Peak Intensities
Pulse-FT NMR distorts intensities of signals.

Pulse-
Therefore, peak heights and areas can be
deceptive.
13- 147
CH3 7 carbons give 7
signals, but
intensities are not
equal
OH
200 180 160 140 120 100 80 60 40 20 0
(, ppm)
Chemical shift (
13- 148
References
fshn..ifas
fshn ifas..ufl
ufl..edu, NA year, Introduction to Spectroscopy,
fshn..ifas
fshn ifas..ufl
ufl..edu/faculty/
edu/faculty/....../lec
/lec08
08..intro_spectr
intro_spectr..ppt
ppt.. Accessed 29
December 2014 2014..
Syafri,, Pn
Syafri Pn.. Suryati Bt Bt.., Hariono
Hariono,, EnEn.. Maywan
Maywan,, 2009
2009,, Infrared Spectroscopy..
Spectroscopy
https:://mnh
https //mnh2020..files
files..wordpress
wordpress..com/ com/2010
2010//04
04/spektro
/spektro--ir
ir..ppt
ppt. Accessed
June 2011
Wolf's, NA year, Infrared spectroscopy, Ultraviolet Ultraviolet--Visible spectroscopy,
Nuclear magnetic resonance spectroscopy, Mass Spectrometry,
www..oglethorpe
www oglethorpe..edu/ edu/...
...wolf/
wolf/...
...//8th
th%%202
202nd
nd%%2020semester/
semester/8 8Chapter
%2013
2013,, Accessed 24 December 2013 2013..
Francis A. Carey, 2003 2003,, Organic Chemistry, Fifth Edition Edition.. Copyright © The
McGraw--Hill Companies, Inc
McGraw Inc.. All rights reserved
reserved..
13- 149

Spectroscopies

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Spectroscopies

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SPECTROSCOPY

is propagated at the speed of light

has properties of particles and waves

Shorter Wavelength () Longer Wavelength ()

Higher Frequency () Lower Frequency ()

Higher Energy (E) Lower Energy (E)

Higher Energy (E) Lower Energy (E)

• Also called thermal

Ex: comets, nebula

Cold, Thin, hot

Compare the dark lines in the middle spectra to

This shows the

Electromagnetic radiation is absorbed when the

Gives information about the functional groups

region of infrared that is most useful lies between

depends on transitions between vibrational

Out of plane Out of plane

3500 3000 2500 2000 1500 1000 500

3500 3000 2500 2000 1500 1000 500

Structural unit Frequency, cm-1

Structural unit Frequency, cm-1

Structural unit Frequency, cm-1 C O

Structural unit Frequency, cm-1

RCH CH2 910--990

R2C CH2 890

R2C CHR' 790--840

Structural unit Frequency, cm-1

3500 3000 2500 2000 1500 1000 500

Structural unit Frequency, cm-1

3500 3000 2500 2000 1500 1000 500

3500 3000 2500 2000 1500 1000 500

• Provide the fingerprint for the sample being

• Rarely used for quantitative purpose since the

Gives information about conjugated  electron

gaps between electron energy

X-axis is wavelength in nm (high energy at left,

200 220 240 260 280

HOMO-LUMO energy gap is affected by

max 170 nm max 188 nm

orange--red pigment in tomatoes

Atom or molecule is hit by high-

Atom or molecule is hit by high-

electron is deflected but transfers much of its

Atom or molecule is hit by high-

electron is deflected but transfers much of its

forming a positively charged, odd-

Molecular ion passes between poles of a

If the only ion that is present is the molecular ion,

The molecular ion dissociates to a cation

The molecular ion dissociates to a cation

Usually several fragmentation pathways are available

Benzene is an example. The major peak

93.4% 6.5% 0.1%

C are 12C 13- 59

Relative visible in peaks for

Relative no m/z 77, 79 pair; H H

One of the first pieces of information we try to

Molecular formula C7H16 C5H8O2

Exact mass 100.1253 100.0524

Knowing that the molecular formula of a

relates molecular formulas to multiple bonds

index of hydrogen deficiency =

1 (molecular formula of alkane –

index of hydrogen deficiency