NMR Skoog - 2019 - 3

Nuclear Magnetic Resonance Spectroscopy Prakash Lamichhane
“Kathmandu University”
“Instrumental Analysis; Skoog (Fifth Edition)”
Introduction of NMR:
• NMR is the most powerful tool for elucidating the structure of organic
compounds.
• Also applicable for Quantitative determination organic and inorganic
species.
• Absorption of radiofrequency in the range 4-900MHz (75-0.5m) cause.
• In NMR nuclei take part in absorption not electron as that in UV and
IR.
• It is used to study a wide variety of nuclei:
1H
13C
15N
19F
1
Nuclear Spin states:

• A nucleus with an odd atomic number or an odd mass number
has a nuclear spin (has quantized spin angular momentum (P)).
• The spinning charged nucleus generates a magnetic field.
Mass no Atomic no Nuclei/Spin q. no. (I) NMR

Odd Odd 1H, 19F (1/2), active Are All nuclei
11B, 35Cl (3/2)
NMR active?
Odd even 13C (1/2 ), 17O (5/2) active

Even Odd 2H, 14N (1) active
Even Even 12C, 16O, 32S (0) in active
2
Splitting of nuclear Spin states:

• Nuclei thus acts like a small bar magnet.
• Magnetic field of the nuclei get divided in different energy levels by strong
magnetic field.
• Nuclei with spin quantum number I is splited into 2I+1 = (+I ……-I) states.
3
• The magnetic fields of

the spinning nuclei will
align either with the
external field, or against
the field.
• Nuclei with opposite spin
possess high energy and
next with align spin will
possess less energy.
• A photon with the right
amount of energy can be
absorbed and cause the
spinning proton to flip.
4
FIGURE 19-1 Magnetic moments and energy levels for a nucleus with
a spin quantum number of 1/2.
5
Energy of spin states, E and effect of B0:

• Energy difference is proportional to the
magnetic field strength.
E = h =  h B0
2
• Gyromagnetic ratio, , is a constant for
each nucleus (26,753 s-1gauss-1 for H).
• In a 14,092 gauss field, a 60 MHz
photon is required to flip a proton. Related
• Low energy, radio frequency. numerical
calculation
 B0 /Absorption frequency MHz

Rad.T-1sec-1 % 1T 1.41T 2.35T 4.7T 7.05T
1 2.6752×108 99.98
1H 42.6 60 100 200 300
6
TABLE 19-1 Magnetic Properties of Important Nuclei
7
Classical description
of NMR:
FIGURE 19-2
Precession of a
rotating particle in a
magnetic field.
8
FIGURE 19-3 Model for the absorption of radiation by a

precessing particle.
9
Population densities in magnetic quantum states: -

Nj
No
 exp  E  kT
    h Bo 
 exp
 2kT 

1.41T & 250c
 - 2.6752X108  6.631034 1.41  1,000,000


 exp 
  0.999991
 2 (1.38 10  298)
 23
 1,000,009
i.e. in approximately two million nuclei only nine nuclei are excess in ground
state. At 4.69T 33 nuclei will be in excess (Make the calculation)
Nj  h Bo Related
Maclaurin expansion  1 numerical
No 2kT calculation
Shows that the relative number of excess low energy

nuclei is linearly related to B0
instruments with high operating frequency are highly
sensitive/can give intense signals). 10
Magnetic Shielding (An environmental effect of NMR Spectra)

• All protons do not absorb the same amount of energy in a given field (B0).
• Electrons that surround the protons also shield them from the external B0.
• Circulating electrons create an induced magnetic field that opposes the
external magnetic field.
• Thus RF absorbed by anucleus is affected by chemical environment (e- and
nuclei)
• Magnetic field strength must be increased for a shielded proton to flip at
the same frequency.
Types of Environmental effect
The first is chemical shift

 It gives the number of
non equivalent nuclei.

 The area gives the
relative number (in low

resolution)
Second is spin- Spin
coupling
 In high resolution
 Will split the peak of its
neighboring proton. 12
NMR Signals
• The number of signals shows how
many different kinds of protons
are present.
• The location of the signals shows
how shielded or deshielded the
proton is.
• The intensity of the signal shows
the number of protons of that
type.
• Signal splitting shows the number
of protons on adjacent atoms.
13
Number of Signals
Equivalent hydrogens have the same chemical shift.
Chapter 13 14
Intensity of Signals
• The area under each peak is proportional to the number
of protons.
• Shown by integral trace.
15
How Many Hydrogens?

When the molecular formula is known, each integral
rise can be assigned to a particular number of
hydrogens.
16
Types of NMR spectra: • Type of instrument

• Types of nucleus
(A) Wide line spectra:
 Radiation source of large bandwidth • Physical state of sample
 At low magnetic field (B0) • Environment of analyte nuclei
 Fine structure is lost (not obtained) • Purpose of data collection
 Single peak for each nuclei species.
 For determination of isotopes or physical environment of absorbing
species.
(B) High resolution spectra:

 Differentiate very small frequency difference 0.01ppm or less
Type of NMR Spectra: a. Wide line
FIGURE 19-11 A low-resolution NMR spectrum of water in a

glass container. Frequency = 5 MHz.
18
FIGURE 19-12(a) NMR spectra of ethanol at a frequency of 60

MHz. Resolution: (a) ~1/106.
19
Type of NMR Spectra:
FIGURE 19-12(b) NMR spectra of ethanol at a frequency of 60

MHz. Resolution: (b) ~1/107.
20
Chemical shift
• The absorbed frequency 0 for shielded and de-shielded
proton will be different.
• Shielded proton absorb at lower frequency
• Shift in 𝜈0 from TMS depends on the magnitude of B0.
• -in 1.41T the 0 of a proton ~ 60MHz
• - in 2.35T it is 100MHz.
• Ratio of shift downfield from TMS (Hz) to total
spectrometer frequency (Hz).
Shift in Hz
 & is expressed in ppm.
Spectroscopy frequency in MHz
• Same value for 60, 100, or 300 MHz machine.

• Called the delta scale/Measured in parts per million.
21
Internal Reference, TMS/DSS
 TMS is added to the sample for the reference.

 Since silicon is less electronegative than carbon, TMS protons are
highly shielded. Signal defined as zero (distinct peak).
 Large number of similar protons => single sharp/ intense peak. TMS
is also Inert, soluble, BP 270c.
 Not soluble in D2O (solvent), in this case DSS is used. Sodium salt
of 2,2-dimethyl-2-silapentane-5-sulphonic acid with deuterated
methylene
 Organic protons absorb downfield (to the left) of the TMS signal.
22
Presence of certain electronic cloud around

Origin of chemical shift: the nuclei generates small induced
magnetic field. This field is proportional to
Applying simple relation, the
applied magnetic field but opposes the app
Absorption freqency and thus the
Chemical shift can be obtained….. field.
 Induced field = Bapp × 𝜎, 𝜎 is screening constant
o  B app (1   )  k (1   )
2 The magnetic field that is reached to nuclei
 o  k .......... ...(i ) Bare proton
is B0 = applied field – induced field
 s  k (1   s )......... ....( ii) Sample Proton
Range of 
 r  k (1   r )......... ....( iii) Reference proton
1
1H 1-13
(iii)  (ii)   r   s  k ( s   r )......... ....( iv)
13
6C 0-220 or more
( r   s )[in Hz]
(iv) /(i )    s   r .......... ..( v) 9F
19 0-800
 o [in MHz]
( r   s )
 Chemical shift in ppm    10 6   s   r  10 6 .......... (vi)
o
23
Delta Scale
24
-  increases from right to left, for TMS  =0
- B0 increases from left to right
NMR scale - Abs Frequency (𝜈0) increases from right to left
25
Location of Signals
• More electronegative atoms
deshield more and give larger
shift values.
• Effect decreases with distance.
• Additional electronegative
atoms cause increase in
chemical shift.
26
Typical Chemical Shift Values
27
Proton Chemical Shift Ranges*

TABLE 19-2
Approximate
Chemical Shifts
for Certain Methyl,
Methylene, and
Methine Protons
29
Factors affecting 
• Electronegativity: Presence of electronegative atom reduce the electron
density around the nuclei, less is the shielding effect, which increases the
δ-value (less is the induced diamagnetic shielding).
• Vander Waals de-shielding: In bulky molecules, proton occupy the sterically
hindered position, the electron cloud of bulky group repel the electron
cloud of proton, thus proton is de-shielded.
• Effect of magnetic anisotropy: space effects of bonds Double and triple
bond have high electron density, and create magnetic field, this field is
stronger in one direction than other and the effect of the field on chemical
shift of nearby nuclei is dependent upon orientation of the nucleus with
respect to the bond.
• Hybridization
• Solvents/ Temperature… 30
Factors affecting 
3.5, 4.5
31
O-H and N-H Signals

• Chemical shift depends on
concentration.
Carboxylic Acid
• Hydrogen bonding in Proton, 10+
concentrated solutions deshield
the protons, so signal is around
3.5 for N-H and 4.5 for O-H.
• Proton exchanges between the
molecules broaden the peak.
Effect of Magnetic Anisotropy
Vinyl Protons, 5.8
Aromatic Protons, 7.3 33

Effect of Magnetic Anisotropy
Acetylenic Protons, 2.9 Aldehyde Proton, 9-10
34
Origins of spin-spin splitting and the coupling constant J:

• The splitting of chemical shift peak occurs, as the magnetic moments
of nucleus interacts (coupling) with magnetic moments of
immediately adjacent nuclei.
• Nonequivalent protons on adjacent carbons have magnetic fields that may
align with or oppose the external field.
• This magnetic coupling causes the proton to absorb slightly downfield when
the external field is reinforced and slightly upfield when the external field is
opposed.
• All possibilities exist, so signal is divided into two or more parts.
Ha Hb Ha Hb
R Ca Cb R R Ca Cb R
R R B0 R R
i, Field of proton b ii, Field of proton is not aligned, decreases
is aligned with B0 B0 at 'a'. Absorbs at low frwequency
35
Effect of Methylene (CH2) protons on CH3 protons

CH3 CH2 OH
Possible spin orientations

of methylene protons.
Field direction
Bo
Both against Both aligned
to the field to the field
no net effect
Effect of B 0 decreases to some extent so, higher
Effect of B 0 increases to some extent so,
field is needed to bring them (methyl proton)
down field occurs.
into resonance and an up field shifts results.
36
CH3-CH2-OH
ETHANOL Effect of CH3 protons on CH2 protons
Possible orientation
of 3 CH3 protons
AC-CX type Two peaks for A

AC-CX2 type Three peaks for A
AC-CX3 type Four peaks for A
Four peaks for A
A2C-CX3 type
Three peaks for X 37
First order spectra are those, where,  >> J, i.e. J/  ≈ 0.05

Second order spectra are those, where J~20Hz, >1000Hz, i.e. J/ ≈ 0.1-0.15
Rules for governing the interpretation of first order spectra :
1. Equivalent protons do not interact with one another to give multiplicity.
2. J decreases significantly with separation of groups. Coupling by a group after three
bonds is not observed.
3. Multiplicity is determined by number of magnetically equivalent proton ‘n’ on the
neighboring atom, which is equal to [n + 1].
4. If proton on B-atom are affected by non equivalent protons on neighboring atoms A
& C. The multiplicity of B protons will be equal to [nA + 1× [nB + 1].
5. Approximate relative area of multiplet peaks are ssymmetric and proportional to
coefficient of (x + 1)n. It is also obtained from PASCAL’s Triangle.
6. Coupling constant is not affected by applied field.(helps to identify splitted peaks
from chemical shift peaks).
7. If interaction occurs between two protons their coupling constant will be same
i.e. J(a,b) = J(b,a), (in some cases helps to identify the neighboring protons) /But J(a,b) = J(c,b) 38
Equivalent protons
• These equivalent protons do not split each other.
• Protons bonded to the same carbon will split each
other only if they are not equivalent.
• Equivalent protons have the same chemical shift.
39
Non equivalent protons

• Have different chemical shift with splitting occurs
40
TABLE 19-3 Relative Intensities of First-

Order Multiplets (I=1/2)
Multiplicity: [1-singlet, 2-doublet, 3-triplet, 4-quartet, 5-quintet, 6-sextet, 7-septet]
41
FIGURE 19-18
Splitting pattern for methylene (b)
Protons in CH3CH2CH2l.
Figures in parentheses are
relative areas under peaks.
(a)=1.02,
(b)=1.86,
(c)=3.17
Second order spectra:
Small coupling constant (J),
around ~20Hz,but large
chemical shift >1000Hz,
i.e. J/ ≈ 0.1-0.15
42
Coupling Constants
• It is the distance between the corresponding peaks of multiplet
• Measured in Hz
• Not dependent on strength of the external field
− Characteristics of two protons which are undergoing coupling.
• Multiplets with the same coupling constants may come from
adjacent groups of protons that split each other.
Saturated alkane
In double bod
Trans olifinic
Cis olefinic
Allylic
Cis
H
H H H H H H
H2C
H H H H
H
J= 6-8 11-18 6-15 4-10 6-10 8-11
Values for Coupling Constants

Effect of Chemical exchange on spectra

• If we consider OH proton in ethanol: Whose spectra are shown below.
• If exchange is rapid; magnetic effect from methylene proton to the OH proton in
alcohol is averaged, and generate a single peak.
• Spin decoupling: Exchange frequency > separation frequency between
interacting group gives give broad line
• Mixture of alcohol and water two peaks/ acid one peak
FIGURE 19-19 Spectrum of highly purified ethanol showing

additional splitting of OH and CH2 peaks (compare with Figure
Hydroxyl
Proton
N-H Proton
• Ultrapure samples of ethanol show splitting.
• Moderate rate of exchange.

• Peak may be broad.
Axial and equatorial protons on

cyclohexane interconvert so rapidly that
• With a small amount of acidic or basic they give a single signal.
impurities will not show splitting.
46
Instrumentation
• CW instrument:
-Sample + CCl4 + TMS
- Spun /all part experience uniform B0.
- 60MHz RF generator/oscillator.
-a detector coil.
-At constant B0: Different protons precesses
at slightly different rates, so absorbs at
different RF
Alternatively: If RF frequency is constant
(60MHz) and B0 is varied, increasing B0
precessional frequency is increased and when
becomes 60MHz it will have resonance.
Strong magnet is capped by electromagnet for
variation of B, varies up to 20ppm.
Instrument which vary the magnetic field continuously from down field end to the up
field end of the spectrum is called continuous wave (CW) instruments or the
frequency domain spectrum.
CW instrument excite only one type of nuclei at a time, until all types of protons come
into resonance.]
FT Spectra
• A short brust of energy (pulse) 1-10ms is
applied from intense RF, 90MHz (2.1T).
• Excites all magnetic nuclei in a molecule
i.e. all proton undergo resonance at the
same time
• The pulse is shown in figure : (a) pulse
sequence; (b) expanded view of RF
pulse.
• The pulse is very short, thus according to
H. uncertainty principle it contains not a
single frequency (90MHz) but a range of
frequency centered at this fundamental
freq.
Frequency 102-103MHz
• Once the pulse is discontinued, during

time T, FID (free inductional decay)
signal is emitted by the
• Once the pulse is discontinued, during time T, FID signal is emitted by the
nuclei. This is recorded by radio receiver coil at perpendicular to static magnetic
field. (Single coil can be used).
• Since a molecule contain many different nuclei; different frequencies are
emitted in decay process and is quite complex.
• When magnetically different nuclei are present, the FID develops a distinct beat
pattern such as that in fig of cyclohexane (C13 NMR) contain three sets of
different carbons.
• The intensity of FID decays with time, which is stored by computer.
• Ordinarily time domain decay signal from numerous successive pulses are added
to improve the S/N ratio.
• This complex time domain signal contain all the information’s required to
produce frequency domain signal
• Individual frequency domain signal is extracted by FT analysis.
If radiation freq.
differs from Larmor
frequency (w0/2p)
by small amount →
The exponential
decay is modulated
by sine wave of
frequency (n-w0/2p)
the diff is =
50Hz
FIGURE 19-9 (a) 13C FID signal for dioxane when pulse
frequency differs
from Larmor frequency by 50 Hz; (b) Fourier transform of
When magnetically different nuclei are present FID has distinct beat pattern
Different between aliphatic C atoms = 62Hz
C13FID signal for cyclohexene
If compound contain many nuclei the absorbance lines/ FID is quite complex
FT converts it to freq. domain

Solvents for NMR

• The solvent used for dissolving sample should have
following properties;
 Should not contain proton,
 Inexpensive
 Low boiling point and non polar in nature.
• Generally deuterated chloroform CDCl3 is used as
solvent.
• If sample is soluble in polar solvent, then deuterium
oxide (D2O), DMSO, CCl4, CS2, Cf3, COOH are used as
solvent.
53
Application of P-NMR
Identification and structure elucidation of organic, M-
organic and biochemical molecules also for quantitative
determinations.
In conjunction with MS, IR, UV and element analysis
procedure compounds can be identified.
Some figures…………………..
…………………………………
FIGURE 19-23 Absorption and integral curve for a dilute

ethylbenzene solution (aliphatic region).
FIGURE 19-24 NMR spectrum and peak integral curve for the
organic compound C5H10O2 in CCI4.
Splitting Tree
a c
H H
C C
Hb
12 13
C-NMR C-NMR
no peak Gives peak
I=0 I=1/2
6P+6N=12 6P+7N=13
Application of 13CNMR:
Chemical shifts are more applied then
coupling constant and splitting.
13
Problems of C-NMR
13
C-NMR signal is 6000 times weaker than1H-NMR signal
NATURAL ABUNDANCE
GYRO MAGNETIC RATIO
COUPLING PHENOMENON
• Natural abundance 1.1%, Small magnetogyric ratio

(about 0.25 as the proton), gives low signals compared
to 1H. Roughly CNMR is about 6000 times less sensitive
than PNMR.
• But using high magnetic field and Fourier transform
instrument signals can be enhanced.
Carbon-13
• 12C has no magnetic spin.
• 13Chas a magnetic spin, but is only low natural
abundance and low gyromagnetic ratio.
• Signals are weak, getting lost in noise.
• Hundreds of spectra are taken, averaged.
FTNMR
• Nuclei in a magnetic field are given a radio-frequency pulse close
to their resonance frequency.
• The nuclei absorb energy and precess (spin) like little tops.
• A complex signal is produced, then decays as the nuclei lose
energy.
• Free induction decay is converted to spectrum. 61
Carbon- 13 NMR: [I=1/2. m= + 1/2]
Advantages over PMNR:
• Provide information’s about backbone of molecule rather than its
periphery.
• Chemical shift for 13C for most compounds extends wide about 200
ppm compared to 10-15 ppm for proton. There is less chance for
the overlap of peaks.
• Homonuclear spin-spin coupling between two C-atoms is not
observed. (Small natural abundance) and hetero nuclear spin
coupling from 12C is nil (I = 0).
• Also number of methods for decoupling the interaction of the
proton are available (give single line).
13C chemical shift, Ran Pages (CDCl3 solution)
Chemical shift effect for 13C is not only determined to the nearest atom, but
within a long chain. For example, The chemical shift at C1 will be 31. 10, 5.3,
0.5, and 0.1 ppm if a chlorine atom is substituted at C1, C2, C3, C4,and C5 of n-
pentane.
FIGURE 19-29 Chemical shifts for 13C.
Hydrogen and Carbon Chemical Shifts
FIGURE 19-29 Chemical shifts for 13C.

Combined 13C and 1H
Spectra
• It is unlikely that a 13C would be adjacent to another 13C,

so splitting by carbon is negligible.
• 13C will magnetically couple with attached protons and
adjacent protons.
• These complex splitting patterns are difficult to interpret.
Broad band decoupling
• Application of broad band radio-frequency signal that
Proton decoupling Methods
encompasses the entire proton spectral region,.
Off-Resonance Decoupling
• In this technique the decoupling frequency is set at
1000 t0 2000 Hz above the proton spectral region to
give partially decoupled spectra.
• 13C nuclei are split only by the protons attached
directly to them.
• The N + 1 rule applies: a carbon with N number of
protons gives a signal with N + 1 peaks.
Nuclear overhauser enhansment (NOE)

• C13 peaks are enhanced much more in decoupling
• Occurs due to coupling from attached decoupled protons
• No increase in sensitivity
2 dimensional FTNMR 67
DECOUPLING THE PROTON SPINS
• A common method used in determining a carbon-13 NMR spectrum is to
irradiate with “noise” all of the hydrogen nuclei in the molecule
continuously at the same time the carbon resonances are being measured.
• This requires a second radiofrequency (RF) source (the decoupler) tuned to
the frequency of the hydrogen nuclei, while the primary RF source is tuned to
the 13C frequency.
• The carbon nuclei see an average of all the possible proton spin states.
• Thus, each different kind of carbon gives a single, unsplit peak.
RF source 1
RF source 2 1H-13C
“the decoupler” pulse tuned to
carbon-13
continuously
saturates
hydrogens
13C signal (FID) measured
68
In this method the hydrogen nuclei are “saturated”,
a situation where there are as many downward as
there are upward transitions, all occurring rapidly.
During the time the carbon-13 spectrum is being

determined, the hydrogen nuclei cycle rapidly between
their two spin states (+1/2 and -1/2) and the carbon nuclei
see an average coupling (i.e., zero) to the hydrogens.
The hydrogens are said to be decoupled from the

carbon-13 nuclei.
You no longer see multiplets for the 13C resonances.

Each carbon gives a singlet, and the spectrum is
easier to interpret.
ETHYL PHENYLACETATE
in some cases
the peaks of the
multiplets will
overlap
13C coupled
to the hydrogens
this is an
13C
easier spectrum
decoupled to interpret
from the hydrogens
SOME INSTRUMENTS SHOW THE MULTIPLICITIES
OF THE PEAKS ON THE DECOUPLED SPECTRA
s = singlet t = triplet
CODE : d = doublet q = quartet
d d
q
s s t
t
d
DEPT Spectra
[Distortionless enhancement by polarization Transfer]
DEPT-135
DEPT-90
DEPT-45
CH CH2 CH3
C normal C-13 spectrum
Quaternary carbons (C) do not show up in DEPT.

73
74
Interpreting 13C NMR
• The number of different signals indicates the number of different
kinds of carbon.
• The location (chemical shift) indicates the type of functional
group.
• The peak area indicates the numbers of carbons (if integrated).
• The splitting pattern of off-resonance decoupled spectrum
indicates the number of protons attached to the carbon.
75
MRI
• Magnetic resonance imaging.

• “Nuclear” is omitted because of public’s fear that it would be
radioactive.
• Only protons in one plane can be in resonance at one time.
• Computer puts together “slices” to get 3D.
• Tumors readily detected.
76
Determine the number of signals in the proton-decoupled
C-13 NMR spectrum of each of the following compounds:
O
O
HO OCCH3
H3C CH3 OCH3
CH3 N
H
CH3
OH OH
CH3
H3C CH3
77
• From the combined
IR, mass, UV, 13C-NMR
and 1H-NMR spectra

given for an unknown
compound elucidate
the correct structure
with the detailed
description Show also
the mass
fragmentation
pattern.
82

NMR Skoog - 2019 - 3

Uploaded by

Copyright:

Available Formats

NMR Skoog - 2019 - 3

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

NMR Skoog - 2019 - 3

Uploaded by

Copyright:

Available Formats

Nuclear Magnetic Resonance Spectroscopy Prakash Lamichhane

Nuclear Spin states:

Mass no Atomic no Nuclei/Spin q. no. (I) NMR

Odd even 13C (1/2 ), 17O (5/2) active

Splitting of nuclear Spin states:

• The magnetic fields of

Energy of spin states, E and effect of B0:

 B0 /Absorption frequency MHz

TABLE 19-1 Magnetic Properties of Important Nuclei

FIGURE 19-3 Model for the absorption of radiation by a

Population densities in magnetic quantum states: -

 - 2.6752X108  6.631034 1.41  1,000,000

Shows that the relative number of excess low energy

Magnetic Shielding (An environmental effect of NMR Spectra)

Types of Environmental effect

The first is chemical shift

non equivalent nuclei.

relative number (in low

 Will split the peak of its

How Many Hydrogens?

Types of NMR spectra: • Type of instrument

(B) High resolution spectra:

Type of NMR Spectra: a. Wide line

FIGURE 19-11 A low-resolution NMR spectrum of water in a

FIGURE 19-12(a) NMR spectra of ethanol at a frequency of 60

Type of NMR Spectra:

FIGURE 19-12(b) NMR spectra of ethanol at a frequency of 60

• Same value for 60, 100, or 300 MHz machine.

Internal Reference, TMS/DSS

 TMS is added to the sample for the reference.

Presence of certain electronic cloud around

Typical Chemical Shift Values

Proton Chemical Shift Ranges*

O-H and N-H Signals

Effect of Magnetic Anisotropy

Vinyl Protons, 5.8

Aromatic Protons, 7.3 33

Effect of Magnetic Anisotropy

Acetylenic Protons, 2.9 Aldehyde Proton, 9-10

Origins of spin-spin splitting and the coupling constant J:

Effect of Methylene (CH2) protons on CH3 protons

Possible spin orientations

AC-CX type Two peaks for A

First order spectra are those, where,  >> J, i.e. J/  ≈ 0.05

Non equivalent protons

TABLE 19-3 Relative Intensities of First-

Values for Coupling Constants

Effect of Chemical exchange on spectra

FIGURE 19-19 Spectrum of highly purified ethanol showing

• Ultrapure samples of ethanol show splitting.

• Moderate rate of exchange.

Axial and equatorial protons on

• Once the pulse is discontinued, during

Different between aliphatic C atoms = 62Hz

C13FID signal for cyclohexene

FT converts it to freq. domain

Solvents for NMR

FIGURE 19-23 Absorption and integral curve for a dilute

GYRO MAGNETIC RATIO