1

INFRARED SPECTROSCOPY
2
In contrast to uItravioIet spectroscopy, the infrared
spectrum provides a rich array of absorption bands
which can provide a weaIth of structuraI information
about a moIecuIe. It provides methods for studying
materiaIs in aII three physicaI states i.e gas, Iiquid or
soIid. AnaIyticaIIy usefuI IR spectrum covers the
foIIowing range of the eIectromagnetic range.
Near IR 15000 cm
-1
to 3000 cm
-1
0.67 m - 3.33 m
Mid IR 4000 cm
-1
to 400 cm
-1
2.5 m - 25 m
Far IR 200 cm
-1
to 10 cm
-1
50 m - 1000 m
Most used 4000 cm
-1
to 670 cm
-1
2.5 m - 15 m
3
Microns or micrometers ( or m) were extensiveIy used
as the units of waveIength in the past but nowadays
wave number (cm
-1
) are the accepted units. A simpIe
reciprocaI reIationship exists between waveIength () and
wave number i.e (cm
-1
) = 10000 / (m). The wave
number is directIy proportionaI to the absorbed energy
(K = E/hc) where as waveIength is inverseIy proportionaI
to the absorbed energy.
v
4
The information contained in an IR spectrum originates
from moIecuIar vibrations. These are either fundamentaI
modes that are associated with the vibrations of specific
functionaI groups, compIex modes of the totaI moIecuIe,
vibrationaI overtones or summationaI modes of
fundamentaI vibrations. IR anaIysis may simpIy invoIve
the characterization of a materiaI with respect to the
presence or absence of a specific group frequency
associated with one or more fundamentaI modes of
vibration or by a compIex pattern recognition or by a
computer search- match aIgorithm when an unknown
spectrum is compared to an existing reference database.
The spectraI data is aIso used to measure one or more
compounds in a simpIe or compIex mixture.
5
A nonIinear moIecuIe containing n atoms has 3n - 6
possibIe vibrationaI modes through which infra red
radiation may be absorbed. For exampIe methane has 9
and benzene has 30 possibIe fundamentaI absorption
bands respectiveIy. In order that a particuIar vibration
resuIts in an absorption band, the vibration must cause a
change in the dipoIe moment of the moIecuIe. Thus
moIecuIes containing certain symmetry groups wiII
dispIay somewhat simpIified spectra. The C=C stretching
of ethyIene and C-H stretching of methane do not resuIt in
an absorption band. Further if absorption occurs outside
the IR region or too cIose for resoIution or too weak in
intensity, the observed number of absorption bands wiII
be Iess than the predicted number .
6
AdditionaI absorption bands may occur because of the
overtones (at 1/2, 1/3 waveIengths with greatIy
reduced intensity), combination bands (sum of two or
more different wave numbers), difference bands (the
difference of two or more wave numbers) etc.
7
MOLECULAR VIBRATIONS
A moIecuIe essentiaIIy resembIes a system of baIIs of
varying masses corresponding to the atoms of a moIecuIe
and springs of varying Iengths corresponding to various
chemicaI bonds. There are two kinds of fundamentaI
vibrations of moIecuIes.
i) Stretching - in which the distance between two atoms
increases or decreases but the atoms remain in the
same bond axis.
ii) Bending - in which the position of the atom changes
reIative to the bond axis.
8
The various stretching and bending vibrations occur at
certain quantized frequencies. When infra red radiation
of the same frequency is incident on the moIecuIe,
energy is absorbed and the ampIitude of that vibration
increases correspondingIy. When the moIecuIe reverts
to the ground state the absorbed energy is reIeased as
heat.
9
MOLECULAR VIBRATIONS
10
MOLECULAR VIBRATIONS- BENDING
11
MOLECULAR VIBRATIONS-BENDING
12
Bending vibrations generaIIy require Iess energy and occur at Ionger
waveIengths (Iower cm
-1
) than stretching vibrations. Stretching vibrations
are found to occur in the order of their band strengths. Thus,
CC 2300 - 2000 cm
-1
4.4 - 50
C=C 1900 - 1500 cm
-1
5.3 - 6.7
C - C
C - N 1300 - 800 cm
-1
7.7 - 12.5
C - O
N - H
C - H 3700 - 2630 cm
-1
2.7 - 3.8
O - H
O - D 2630 cm
-1
3.8
O - H 3570 cm
-1
2.8
13
An approximate vaIue of the stretching frequency in
(cm
-1
) of a bond can be caIcuIated by the reIationship,
where k is a force constant (~ 5,10,15 x 10
5
dynes/cm
for singIe, doubIe and tripIe bonds), M
X
and M
Y
are the
masses of the atoms in grams.
X X
1 k
=
2 M / M
Y Y
c M M
v
t +
v
14
INSTRUMENTATION
Modern commerciaI infrared instruments faII into three
categories: Grating dispersive, fiIter dispersive and
Fourier Transform (FT) infrared spectrometers.
EssentiaIIy the infrared instruments consists of the
foIIowing components:
i) The main opticaI system
ii) The source
iii) SampIe compartment
iv) The detector and
v) The eIectronics and data handIing
15
Whatever the mode of operation, spectrometer or the
spectrophotometer forms the heart of the instrument. It
takes the broad band infrared radiation and spIits it
into uItimate discrete frequencies or waveIengths with
a given spectraI resoIution. This may be performed
directIy with a monochromator in a dispersive
instrument or indirectIy by a Fourier Transform
instrument. In Fourier Transform, an interferometer
assembIy known as 'moduIator' produces an output in
the form of a moduIated infrared beam which is
decoded to produce the finaI infrared spectrum.
16
MONOCHROMATOR INSTRUMENTS
Monochromators range from simpIe fiIter based instruments
to high resoIution, doubIe prism/grating /grating systems.
Both Littrow and Czerney- Turner mountings are usefuI
aIthough the former is most usefuI. EarIier instruments were
mostIy prism based which provided a simpIe waveIength
scan in micrometers. Nowadays Iittrow designs with one or
more diffraction gratings are used. The gratings are driven
by a stepping motor which is programmed into non Iinear
fashion to produce a Iinear output in wave numbers.
17
The fuII range of a grating spectrometer may be
4000 - 600 cm
-1
or 5000 - 200 cm
-1
. Gratings are normaIIy
operated in second or third order. UsuaIIy spectrums in
the 4000 - 2000 cm
-1
range is operated in second order
and 2000 - 400 cm
-1
range is obtained in the first order. A
series of cut off and bandpass fiIters are pIaced between
the monochromator and the detector to ensure the correct
order of the grating. This is achieved by synchronizing
with the scanning of the grating. In more expensive
instruments onIy first order grating is used for aII the
gratings to provide optimum performance which is
maximum over aII the output range.
18
A grating bIazed at two angIes performs as two gratings
in one. The drive is reproducibIe by 0.01 cm
-1
but it can
aIso be precaIibrated against a spectroscopic standard.
Modern monochromators are directIy driven by a stepper
motor and microprocessor controIIed to provide high IeveI
of accuracy. This aIso provides a sIit programming
mechanism to give near constant energy.
SingIe beam photometers posses the capacity for accurate
measurement in quantitative anaIysis.
19
FOURIER TRANSFORM
INTERFEROMETER
20
21
NON-INTERFEROMETRIC IR SPECTROSCOPY
USING NO MOVING PARTS
22
Instead of using a monochromator, the IR radiation after
passage through a sampIe can be anaIysed by means of
a scanning MicheIson interferometer. It consists of a
moving mirror, a fixed mirror and a beam spIitter.
Radiation from the infrared source B is coIIimated by a
mirror, spIit into two beams. One beam is passed through
a fixed mirror and another to a moving mirror. After
refIection the two beams are recombined at the beam
spIitter. The two beams interact at any particuIar
waveIength constructiveIy or destructiveIy depending on
the difference in the opticaI paths.
23
The intensity of the emerging radiation moduIates in a
sinusoidaI manner. In the case of a broad band infrared
source the emerging beam is a compIex mixture of
moduIation frequencies, which after passing through the
sampIe compartment is focused onto the detector.
The detector signaI is sampIed at very precise intervaIs
during the mirror scan. Both the sampIing rate and mirror
veIocity are controIIed by a reference signaI from the
detector produced by the moduIation of the beam from a
He - Ne Iaser. The resuIting signaI is known as an
interferogram which contains aII the information required
to reconstruct the spectrum using a mathematicaI process
known as Fourier Transformation.
24
ADVANTAGES OF FTIR
i) OnIy one moving part is invoIved which is mounted
on a frictionIess air bearing.
ii) SIits and fiIters are not needed which saves energy
especiaIIy in the far IR region.
iii) Near absoIute frequency accuracy (better than 0.01
cm
-1
).
iv) Same S/N ratio as in a dispersive spectrometer
obtained in a fraction of time (FeIIgets advantage).
v) Saves time as many as 32 scans can be done per
minute.
vi) SingIe beam spectrum is ratioed against stored
background in the memory which gives the doubIe
beam accuracy.
25
To appreciate how the interferometer works and how it
can be reIated to a spectroscopic measurement, Iet us
see what happens with a singIe waveIength in an
interferometer.
26
At position 1, the moving mirror and fixed mirror are
equidistant from the beam spIitter. In this situation
both Iight beams traveI the same distance and when
they recombine at the beam spIitter they are mutuaIIy
in phase and constructive interference occurs. This is
observed as a maximum signaI being passed through
to the detector. Let this signaI be unity (zero path
difference).
27
SCHEMATIC FTIR DIAGRAM
source
28
As the mirror moves away from ZPD (zero position
dispIacement) to 1/4 , the signaI reaches a minimum
vaIue or zero (out of phase). Further on, when it reaches
1/2 OPD (opticaI path difference), it again reaches a
maximum vaIue with constructive interference. This
pattern continues where a series of maxima and minima
are produced at /4 and /2 to yieId an overaII sine wave
pattern or more accurateIy, a cosine wave.
If a second waveIength is seIected now, a simiIar wave
form is generated but the maxima and minima are
separated by a distance equivaIent to the new
waveIength.
29
In this way a unique cosign wave is generated for each
waveIength. The observed signaI at the detector is a
summation of aII these cosign waves which gives a
maximum at ZPD and rapidIy decays to a compIex
overIapped signaI which continues to decay with
increasing distance from ZPD.
If the component cosign waves can be resoIved then
the contribution from individuaI waveIengths can be
observed and a spectraI output of the source couId be
constructed. This function is performed mathematicaIIy
by a Fourier Transformation for frequency anaIysis.
30
In mathematicaI terms, the Fourier reIationship is
defined as a pair of integraIs.
where I() is the intensity of the interferogram as a
function of retardation and B( ) is the source intensity
as a function of the wave number.
o o v t o v
v o v t v o
d 2 cos ) ( ) ( B
and d 2 cos ) ( B ) ( I
-
-
}
}

=
=
I
v
31
An ideaIized interferogram has a unique centre burst
corresponding to ZPD with maximum intensity at the
centre than on either side. As the sampIe is introduced,
the distribution of information changes depending
upon the naturaI Iine width of infrared spectrum of the
sampIe and consequentIy more signaI is observed in
the wings of the interferogram.
32
INTERFEROGRAM SINGLE BEAM SPECTRUM
33
SpectraI resoIution of an IR instrument can be defined
as the abiIity of the monochromator to separate two
spectraI features such as peaks or troughs or the abiIity
to observe the separation of discrete waveIengths. This
transIates into the abiIity to define two cosine waves of
different frequencies when they go out of phase and
remain in phase at Ieast once i.e 1/ cm, where
Maximum resoIution of a spectra is approximateIy
defined as 1/
max
, where
max
is the distance of the
moving mirror. Once data is obtained at a specific
resoIution, spectrum of Iower resoIutions can be
artificiaIIy generated by using a subset of the data or
by extrapoIation.
v
) ( -
1
1 2

= A cm v v v
34
TheoreticaIIy the information shouId be coIIected at
infinite retardation but in practice the data is acquired
at practicaI distances which resuIts in the truncation
of the interferogram at some stage and hence the
separation wiII be aIways Iower than the predicted
vaIue. This is known as apodization.
Thus an apodizing function needs to be appIied to
reduce the effect of premature truncation of the data.
This acts Iike a weighting function. Two apodizing
functions such as Hanning or Happ-GenzeI are popuIar.
This aIso reduces the noise since the noise is aIways
uniformIy distributed through out the interferogram.
35
The signaI produced is aIso a phase dependent
phenomenon. OpticaI components that can cause
dispersion (mirrors) , beam spIitter, detector etc., can
aIso introduce phase errors in the finaI spectrum. Thus
phase corrections are aIso normaIIy appIied to reduce
the photometric errors.
36
SAMPLE HANDLING
Infrared instrumentation has reached a remarkabIe degree
of standardization but sampIe handIing itseIf presents
a number of probIems. No rugged window materiaI for
cuvettes exist that is transparent and inert over the
entire infrared region.
AIkaIi haIides such as NaCI are wideIy used since they are
transparent up to 625 cm
-1
. CeII windows are easiIy fogged
by exposure to moisture and require frequent poIishing.
GIass and quartz absorb strongIy in infrared region, so
they can not be used as ceII containers or opticaI prisms.
37
AImost invariabIy in aII dispersive instruments, the
sampIe compartment is positioned before the
monochromator to conserve weak IR energy and
reduce stray radiation and opticaI aberrations.
AgCI is often used for moist sampIes but it is not entireIy
satisfactory. It easiIy deforms, is too soft and darkens on
exposure to Iight. For frequencies under 600 cm
-1
, a
poIyethyIene ceII is usefuI. Characteristics of other usefuI
window materiaIs are shown in the next tabIe.
38
TabIe1. IR TRANSMITTING MATERIALS
Window materiaI UsefuI frequency
NaCI 40000 - 625 cm
-1
KBr 40000 - 400 cm
-1
AgCI 25000 - 435 cm
-1
AgBr 20000 - 286 cm
-1
CaF
2
6670 - 1110 cm
-1
BaF
2
50000 - 870 cm
-1
CsBr 10000 - 270 cm
-1
ZnSe (Vacuum deposited) 10000 - 55 cm
-1
PoIyethyIene 625 - 33 cm
-1
39
Gases can be directIy scanned in 10 cm pathIength
ceIIs. For trace anaIysis, ceIIs of 1.5 - 120 meter are
used. Such ceIIs are constructed with foIded Iight
paths and goId surfaced mirrors.
Liquid sampIes are usuaIIy scanned in their neat form
or in soIution. The sampIe thickness shouId be
0.001 - 0.05 mm thickness which provides transmittance
of 15 - 70%.
40
For soIutions, a 10% carbon tetrachIoride(CCI
4
) is ideaI
for 4000-1333 cm
-1
range. Carbon disuIphide(CS
2
)
is usefuI for 13333 - 650 cm
-1
. MethyIene chIoride,
acetonitriIe and acetone are the other usefuI soIvents.
IR ceIIs are constructed with seaIed windows which are
separated by thin gaskets copper and Iead gaskets
which are wetted with mercury. The whoIe assembIy is
secureIy cIamped in a stainIess steeI hoIder. As the
mercury penetrates a gasket it expands producing a
tight seaI.
41
FILMS
For poIymers, resins and amorphous soIids the sampIe
is dissoIved in a voIatiIe soIvent and a drop of the
soIution is pIaced on the window and seaIed. As the
soIvent evaporates, a thin homogeneous fiIm is
deposited which can be scanned directIy. For Iiquids
and poIymers a drop of the soIution may be pIaced and
squeezed between the windows.
42
MULLS
Powders can be examined as a thin paste or muII.
About 5 mg of the sampIe is mixed with nujoI (a high
moIecuIar weight Iiquid paraffin). NujoI has peaks
around 3030 - 2860, ~ 1460 cm
-1
and 1374 cm
-1
.
Therefore no usefuI information can be obtained in
these regions. HexachIorobutadine is another
muIIing agent. It has no CH bonds.
A soIid sampIe can aIso be handIed by mixing with
KBr and pressing at 25000 psi into a smaII disc of
10 mm diameter and 2mm thickness. Quantitative
anaIysis can be performed by the peIIet technique .
43
RADIATION SOURCES
Most commerciaI instruments use an extended source
cIose to that of a bIack body radiation around
1000-1500 K. Nicrome wire, the Nerst gIower, the
Opperman and GIober sources are commonIy
empIoyed as sources of IR radiation.
Nichrome wire is either a simpIe coiI or supported on a
ceramic rod. Low and mid priced instruments use this.
It is easy to maintain and repIace. ProIonged use can
Iead to oxidation and thermaI stresses deform the
coiI shape. Thus Iong term stabiIity and output are
affected.
44
Nernst gIower is composed of a mixture of rare earth
oxides that are heated by eIectric current. This has a
negative coefficient of eIectricaI resistance. Its eIectricaI
conductivity increases with increasing temperature.
Therefore externaI heating is required to start the fIow of
eIectricity and it must be carefuIIy reguIated to controI a
'run away' situation.
The Opperman consists of a ceramic rod fiIIed with rare
earth oxides with a coaxiaI metaI wire Iocated inside
the centre. The wire is heated first which in turn heats
the oxide mixture. This is seIf reguIating and does not
require externaI heating.
45
The GIober is essentiaIIy an eIectricaIIy heated siIicon
carbide rod capabIe of being operated at high
temperatures. In most cases externaI water cooIing is
essentiaI to heIp stabiIize the source and to reduce the
heat dissipation to other components in the
instrument.
TypicaI Iife spans are around 2 - 5 years. The most
common faiIures are fractures or hot spots or Ioss of
power by oxidation of eIectricaI connections.
46
DETECTORS
ThermaI detectors or photon sensitive (quantum)
detectors are usefuI in IR. ThermaI detectors sense
temperature changes by a change in physicaI property
such as generation of voItage or change in resistance.
The speed of thermaI detectors are infIuenced by the
thermaI or heat capacity of the detector eIement which is
somewhat Iower than photon counting detectors. But the
response of thermaI detector is independent of the
waveIength of the incident radiations.
47
The thermocoupIe, the pneumatic or GoIay detector
and boIometer are of thermaI detector type. IR response
temperature changes are of the order of 10
-3
to 10
-2
K.
These are used extensiveIy in dispersive type instruments
and boIometers are used in FT- IR instruments.
48
The thermocoupIe is fabricated with two dissimiIar
metaIs such as bismuth and antimony which produce a
smaII voItage proportionaI to the temperature of
junction. SeveraI thermocoupIes are connected in series
for additionaI output. HaIf of the junctions are 'hot'
containing the active eIement. AIternate junctions are
'coId' that are thermaIIy bonded to the substrate and
remain at a reIativeIy Iower temperature. Thin fiIm
techniques have miniaturized the thermocoupIes. The
entire assembIy is mounted on an evaIuated encIosure
with IR transmitting window. So that conductive heat
Iosses are minimized. The response time is about 80sec.
49
CROSS SECTION OF A THERMOCOUPLE
DETECTOR
50
WAVELENGTH RESPONSE OF SOME IR
DETECTORS
1. INSB at 77 K
2. PBSNTE at 77 K
3. PBSNTE at 42 K
4. PyroeIectirc at 300 K
5. Thermistor at 300 K
6. ThermopiIe at 300 K
51
A thermistor functions by changing resistance when
iIIuminated with IR. These are made of sintered oxides
of manganese , cobaIt and nickeI and have a high
coefficient of resistance (4% / C
0
). One of these is
'active', which is coated bIack and mounted to
increase its IR absorption whereas reference is
opticaIIy shieIded to prevent IR exposure. Both are
mounted on an insuIating substrate pIaced on a heat
sink. When connected with a bridge circuit, it
compensates the ambient temperature drifts. The
response times are a few miIIiseconds.
52
The GoIay pneumatic detector uses the pneumatic
expansion of a gas as the measuring device. The unit
consists of a smaII metaIIic cyIinder cIosed by a rigid
bIackened metaI pIate (2mm square) at one end and a
fIexibIe siIver diaphram at the other end. The chamber is
fiIIed with xenon. The radiation absorbed by the
bIackened pIate causes the gas to expand and deform
the diaphragm which in turn obstructs the Iight path
faIIing on a phototube. The distortion aIters the pIate
separation and hence the capacity. Response time is
20 msec(simiIar to TC). It is best among the Iot.
GOLAY PNEUMATIC INFRARED DETECTOR
54
PHOTON DETECTORS
These are more sensitive. Photons incident on a
semiconductor produces eIectrons and hoIes
(InternaI photoeffect). A sufficientIy energetic
photon raises the eIectron to conduction band.
In a photoconducting detector, the presence of
eIectrons in the conduction band wiII Iower the chips
resistance. Intrinsic hoIe-eIectron pairs are created by
raising the eIectron to conduction band of the
semiconductor. Extrinsic excitation refers to eIectrons
raised from or to impurity doping IeveIs within the
forbidden band of the semiconductor. A bias current or
voItage registers this change as output.
55
PhotovoItaic detectors generate a smaII voItage in
In-Sb p-n type junction in singIe crystaIs. The p type is
Iaid as a thin Iayer over n type . The band gap is 0.23 ev
at Iiquid nitrogen temperature.
Lead-tin-teIIuride detectors extend spectraI sensitvity
to considerabIy Iarger waveIenths than In-Sb .i.e. 5-13 m
and 6.6-18 m. When used with a current mode ampIifier
response time is of the order to 20 nanoseconds.
56
APPLICATIONS OF IR
1. In generaI IR peaks wiII occur at the same frequencies
for specific groups except in moIecuIes where steric or
eIectricaI effects are predominant. For exampIe carbonyI
(C=O) stretching vibration is same for acetone or
di-n-hexyIketone. But it is different for acetic acid
(eIectricaI effect) and for cycIobutane (steric effect).
AIso IR spectrum can not distinguish a pure sampIe from
impure sampIe. Thus a crude product wiII show infrared
peaks of aII the reactants and side products. Even high
moIecuIar weight chemicaIs generaIIy give poor spectra.
57
2. The progress of a chemicaI reaction can be foIIowed
by drawing an aIiquot and checking the IR spectra for
a specific functionaI group. ChemicaI separations
aIso can be foIIowed by the same principIe.
ExampIe :
OH frequency 3570 cm
-1
decreases and C=O appears
at 1725 cm
-1
.
R
1
R
2
CH - OH
R
1
R
2
C = O
58
3.The most powerfuI function of IR is in estabIishing
the identity of a sampIe by comparison using same
medium. The region 1430 - 910 cm
-1
contains many
C - C , C - O, C - N stretching vibrations and bending
vibrations. This is known as finger print region. Thus
even if simiIar compounds show simiIar spectra,
discernibIe differences can be identified in the finger
print region.
59
SeveraI compiIations are avaiIabIe Iisting characteristic
group absorptions which can be used to characterize
an unknown materiaI. Thus if a compound shows a peak
at 1718 cm
-1
, it certainIy contains a C=O group. But it
couId be an aIdehyde (CHO), a ketone (C=O), an amide
(NHCO), an ester(RCOOR
/
) or an acid (COOH). Further
anaIysis of IR spectra or cIassicaI techniques are
required to identify the compound.
But if the IR spectrum does not contain (1850 - 1587 cm
-1
)
1718 cm
-1
peaks, it has no C=O group.
60
Given beIow are easiIy interpreted absorption bands
of some common organic compounds. It is important to
account for peaks that are not of the anaIyte e.g NujoI.
This shows C-H stretching (2950, 2820 cm
-1
) , -CH
2
bending (~ 1458 cm
-1
), C - CH
3
bending (~ 1458, 1380 cm
-1
)
and -(CH
2
)- stretching (722 cm
-1
). These peaks need to be
discounted whiIe interpreting the spectra.
II
1) CH
3
- (CH
2
)
10
- CH
2
OH CH
3
- (CH
2
)
2
- (CH
2
)
10
- CH
3
(O - H, 3448 cm
-1
) 1758 cm-1 and 1110 cm
-1
C - O(st) 1053 cm
-1
C - O (st)
O
61
2) in CCI
4
OH(st) 3788 cm
-1
OH 3571 cm
-1
In diIute CCI
4
, 3788 cm
-1
peak is more prominent
compared to 3571 cm
-1
.
3) C = O ketones 1754 - 1667 cm
-1
cycIohexanones 1715 cm
-1
- 1720 cm
-1
cycIopentenone 1745 cm
-1
pentanone 1751 cm
-1
OH
62
4) The effects of ring size and conjugated unsaturation
seem to be additive.
A haIogen on C atom to C=O raises the frequency by
about 20 cm
-1
.
5) C=O group in aIdehydes aIso shifts to Ionger
waveIength with C-H conjugation.
But in C C-H (st) 2940 cm
-1
BenzaIdehyde - 2841 and 2762 cm
-1
C-H stretching
3086 cm
-1
for aromatic C-H stretching
H
O
63
6) CarboxyIic acid anhydrides show two absorption
bands in 1870 - 1740 cm
-1
. Shorter waveIength is
more intense.
7) AC
2
O 1832 cm
-1
and 1761 cm
-1
C=O
1175 - 1050 cm
-1
for C-O (stretching)
8) Amides 1786 - 1626 cm
-1
C=O
1718 cm
-1
C=O stretching (in vapour state)
1650 cm
-1
in pure Iiquid
1701 cm
-1
in chIoroform
3570 - 312 cm
-1
N - H stretching two
peaks for 1
0
, one peak for 2
0
and
no peak for 3
0
amines.
64
9) Amines 3570 - 3333 cm
-1
N - H stretching
1658 - 1608 cm
-1
N - H bending
The moIar extinction coefficients of functionaI groups
can not be accurateIy determined since the path Iengths
can not be exactIy measured. But average vaIues can be
caIcuIated. For exampIe, for the CO group the foIIowing
moIar extinction coefficients have been obtained.
500 (aIdehyde)
800 (acid)
1300 (amide)
Thus for weak absorptions more quantity is required.
65
10) AIkenes C=C 1680 - 1620 cm
-1
(weak)
C-H 3135 cm
-1
for C-H (stretching)
Cis and trans forms can be identified by different
bending vibrations.
11) AIkynes CC 2275 - 2085 cm
-1
(weak)
3333 C-H (stretching)
CN In the same region but more
intense.
66
12) Aromatic compounds .
C-H stretching ~ 3030cm
-1
, ~ 1600, 1580, 1500 and 1450 cm
-1
C=C in pIane 1000 - 670 cm
-1
CH bending
Monosubstituted aromatic rings show very characteristic
IR peaks at 750 and 700 cm
-1
.
Disubstituted aromatic rings show very characteristic IR
peaks at 5730 cm
-1
and 2000 - 1670 cm
-1
which are
overtone bands of Iow intensity.
TabIe 2: IR peaks for some characteristic
functionaI groups
67
TabIe 2.
68
TabIe 2 .
69
TabIe 2.
70
TabIe 2.
71
TabIe 2.
72
TabIe 2.
73
TabIe 2.
74
TabIe 2.
75
DI-N-BUTYL ETHER
76
LAURYL ALCOHOL
77
ISO BORNEOL IN CARBON TETRACHLORIDE
78
CYCLOHEXANONE
79
CYCLOPENTANONE
80
ETHYL BENZOATE
81
BUTYRO LACTONE
82
ETHYL ACETOACETATE
83
NONANOIC ACID
84
BENZOIC ACID
85
86
IR GAS ANALYSERS
AnaIysis for singIe gas component can be carried out
by using a simpIe IR fiIter photometer.
87
The energy is spIit into two beams directed towards
boIometers wired in a baIanced circuit. The sampIe gas
fIows through a ceII that extends across both beams.
One beam passes through a fiIter ceII and the other
one through a compensating ceII. FiIter ceII contains
pure gas being anaIysed and compensating ceII
contains a gas simiIar to that being anaIysed.
For exampIe the anaIysis of ethyIene, ethane and
methane, three waveIengths can be seIected in the IR
region. If a fiIter ceII is fiIIed with ethyIene, aII IR
absorbed by C
2
H
2
wiII be compIeteIy eIiminated from B
1
and aIso from the sampIe.
88
SimiIarIy interference of methane is eIiminated by
pIacing pure methane in the interference ceII which
fiIters out from both beams the waveIengths absorbed
by methane. Thus onIy ethyIene is determined using
this arrangement from 0 - 10% in a sampIe gas.
89
Another arrangement is shown here. Both D and D
I
are
identicaI containing a sampIe of the gas being determined.
UsuaIIy diIution is carried out using argon to reduce
specific heat. The vesseIs are separated by a diaphragm
and one of them is pierced by a hoIe. The intact diaphragm
is free to bend in response to variation in the pressure.
This causes a change in the eIectricaI capacitance between
D and other pierced diaphragm D
I
.
The pressure in D and D
I
depends on temperature
which is in turn dependent upon the IR absorbed. The
reference ceII is fiIIed with dry nitrogen and seaIed off.
The two diaphragms of the detector constitute a
capacitor which is incorporated in a high frequency
eIectronic circuit which eventuaIIy energizes a smaII
motor to drive a baIancing vane across the reference
beam tiII they match. The amount of compensation is
recorded as a signaI.
90
91
DETECTION LIMITS OF SOME GASES BY NON
DISPERSIVE INFRARED SPECTROMETER
CO 1.0 moIe%
CO
2
0.1
SO
2
0.1
NH
3
5.0
CH
4
1.0
C
2
H
6
0.1
C
4
H
10
0.1
C
2
H
2
1.0
C
3
H
6
0.05
92
QUANTITATIVE ANALYSIS
Quantitative IR anaIysis is based on Beer's Iaw.
ChemicaI and instrumentaI effects may cause apparent
deviations and aIso high vaIues of absorbances. Since
the energy is quite smaII, it is necessary to use rather
wide sIit which introduces errors in the moIar
absorptivities. Hence it is onIy empiricaI. UsuaIIy base
Iine method is empIoyed for quantitative anaIysis.
BASE LINE MEASUREMENT TECHNIQUE
93
94
In this method a suitabIe IR band is seIected. Incident
radiant energy P
o
is obtained by drawing a tangent
to spectraI absorption curve. The transmittance P is
measured at the point of maximum absorption. The
vaIue of Iog P
o
/P is pIotted against concentration. Since
the same ceII is used for aII determinations many
possibIe errors are eIiminated.
For soIids, KBr peIIets of known weights mixed with
various quantities of the anaIyte are used. An internaI
standard of KSCN at 0.2% by weight of KBr is used and
the ratio of SCN
-
at 2125 cm
-1
to a chosen band
absorbance is pIotted against concentration.
IR SPECTROPHOTOMETER
95
MASS SPECTROMETRY
1
Mass Spectrometry is the most accurate method for the
determination of the mass of a moIecuIe and its eIementaI
and isotopic composition. Mass spectrometry is aIso
extremeIy usefuI in the determination of the structure of
moIecuIes. In mass spectrometry moIecuIes are converted
into ions which are separated by eIectric and magnetic fieId
gradients on the basis of their mass/charge ratios and
detected.
2
When a moIecuIe is bombarded with a beam of energetic
eIectrons under controIIed conditions it is converted
IargeIy into a singIe positiveIy charged moIecuIar ion.
That is, one eIectron is knocked off from the moIecuIe.
The mass/charge ratio of this is simpIy the moIecuIar
mass of the ion.
Ex:
3
+
The moIecuIar ion (M
+
) breaks up into smaIIer units by
a process known as fragmentation. The fragments
which are positiveIy charged are caIIed daughter ions
and the moIecuIar ion is known as the parent ion. A
signaI is obtained for each m/e. The intensity of each
signaI represents the reIative abundance of the ion
producing the signaI. The peak whose intensity is
maximum in the spectrum is arbitrariIy assigned a
vaIue of 100% and is IabeIed as the base peak. The
intensities of other peaks are presented reIative to the
base peak. The base peak shouId not be confused with
the moIecuIar peak.
4
The mass spectrum is a graphic pIot of the intensity
versus m/e ratio. No two compounds can have exactIy
simiIar mass spectra. Therefore, the mass spectrum of
a compound can be used as a finger print. Very smaII
amounts of sampIe are required for mass spectrometric
anaIysis. Mixtures can be anaIyzed easiIy. The method
is accurate, highIy sensitive and reproducibIe. It is aIso
usefuI fro unraveIing the reaction mechanisms and the
identification of functionaI groups in organic compounds.
It is used in stabIe isotope tracer techniques in research.
5
In a mass spectrometer a moIecuIe M is bombarded with high
energy eIectrons of the order of 70 ev ( 6688 k J moIe
-1
).
This is the typicaI bond energy of organic moIecuIes. When
the energy of the bombarding eIectrons is equaI to the
ionization energy of the moIecuIe, one eIectron is knocked off
from the moIecuIe to produce the moIecuIar ion.
M + e
-
M
+
+ 2e
-
Ionization
energy
6
If the energy of the bombarding eIectrons are much
higher than the ionization energy of the moIecuIe some
bonds in the moIecuIe wiII rupture forming a new ion N
+
and a fragment R. The minimum potentiaI (used for
acceIerating the bombarding eIectrons) required to
effect fragmentation is known as appearance potentiaI of
the fragment ion. Further increase in the potentiaI may
Iead to more fragmentation into smaIIer ions and neutraI
fragments. For the parent ion m/e equaIs the moIecuIar
mass because mass of an eIectron is negIigibIe.
7
The positiveIy charged ions traveI towards the detector
and give rise to sharp Iines at their respective m/e
vaIues. The detector is an eIectrometer with eIectric
and magnetic focussing devices.
8
From the patterns obtained from pure compounds and
that given by the sampIe, considerabIe information can
be generated regarding the structure or composition of
the sampIe. It is possibIe to obtain spectra of the
negative ions but eIectricaIIy neutraI fragments can not
be detected in a mass spectrometer.
9
The basic units of a mass spectrometer are:
A sampIe introduction system to produce a jet of
vapour from the sampIe.
An ion source to produce ions from the sampIe
moIecuIes.
A mass anaIyzer to separate the ions according to their
m/e ratios.
An ion coIIector and ampIifier to act as a detector.
A recorder to record the spectrum.
A high vacuum system from ion source to the detector.
10
SCHEMATIC DIAGRAM OF A MASS
SPECTROMETER
11
SAMPLE INTRODUCTION
SampIe introduction can be achieved by any one of the
foIIowing methods:
1. The sampIe is converted into a spark eIectrode and kept
in the ion source.
2. A smaII amount of sampIe is coated on a fiIament and
heated within the ion source.
3. 100 g to 1 ng sampIe is directIy introduced into the ion
source (The sampIe must be sufficientIy voIatiIe for this).
12
4. Gases can be introduced from a gIass buIb, aIIowed
to expand into a reservoir and the required quantity
is aIIowed to fIow into the ion chamber. Liquids can
be introduced using micro pipettes or syringes.
SoIids having meIting points beIow 200
0
C can be
introduced in the same way because the reservoir is
kept heated.
5. High meIting inorganic materiaIs can be pIaced in a
furnace ceII caIIed 'Knudsen CeII' cIose to the ion
source and the vapours may be aIIowed to pass into
the ion chamber.
13
In the case of ion source, sampIes that are sufficientIy
voIatiIe ions may be produced either by EIectron
Impact (EI) or by ChemicaI Ionization (CI).
In eIectron impact technique a heated tungsten fiIament
emitting eIectrons which are acceIerated by appIying a
potentiaI difference of 70 V. The kinetic energy of the
eIectrons wiII be equaI to 70 ev which is sufficient to
ionize most organic moIecuIes.
14
ION SOURCE
The most probabIe reaction is
M + e M
+
+ 2e.
M
+
wiII then undergo extensive fragmentation
reactions. Often the moIecuIar ion Iine wiII be missing
in the spectrum.
15
ELECTRON IMPACT SOURCE
16
In chemicaI ionization technique, a reagent gas Iike
isobutane, methane or ammonia is Iet into the ion
chamber at a pressure of about 10
2
Nm
-2
and ionized by
bombarding with eIectrons having kinetic energies up
to 300 ev. The sampIe moIecuIes are voIatiIized into
fragmented reagent ions which can aIso protonate the
sampIe moIecuIes.
M + CH
5
MH
+
+ CH
4
The observed m/e wiII be one unit more than the
moIecuIar weight.
+
17
SCHEMATIC DIAGRAM OF C.I SOURCE
18
The internaI energies of MH
+
ions decreases in the order
CH
5
> C
4
H
9
> NH
4
.
This means, when CH
5
transfers a proton to a moIecuIe M
to form MH
+
, much energy is Iiberated because M has
greater affinity for H
+
than CH
4
. The Iiberated energy can
cause fragmentation of MH
+
. NH
4
has the Ieast internaI
energy in the above. This is because NH
3
has great affinity
for H
+
. If at aII it transfers H
+
, there wiII be IittIe excess
energy to cause further fragmentation of the sampIe
moIecuIes.
+ + +
+
19
+
Thus ammonia chemicaI ionization is an exceIIent
method for determination of the moIecuIar weights of
unknown moIecuIes. Negative ion spectra can be
produced by chemicaI ionization method. ChemicaI
ionization can be used for nonvoIatiIe substances aIso.
20
For nonvoIatiIe substance ionization methods incIude fieId
desorption (F, D) fast atom bombardment (FAB), caIifornium
pIasma desorption (CFPD), Iaser desorption (LD) and photon
ionization (PI).
In fieId desorption method, a soIution of the sampIe is
smeared on a heated wire maintained at 8000 V. EIectrons
are transferred from the sampIe to the wire metaI and positive
ions (M
+
) are desorbed by eIectrostatic repuIsion. The ions
may coIIide to form MH
+
.
In Iaser desorption the (soIid or the soIution of the sampIe in
a nonvoIatiIe Iiquid) sampIe is irradiated with a Iaser beam.
Energy absorbed by the sampIe voIatizes and ionizes it.
21
In the fast atom bombardment method, the sampIe is
dissoIved in a soIvent Iike a gIyceroI homoIogue and
bombarded with a beam of fast xenon atoms. The fast
Xe atoms are produced by acceIerating Xe
+
to 6-9 kev
and then neutraIizing these by eIectron transfer.
Xe
+
+ Xe Xe + Xe
+
The sampIe is desorbed as an ion by momentum transfer.
22
In
252
Cf pIasma desorption,
252
Cf undergoes spontaneous
fission giving rise to
142
Ba
18+
(79 Mev) and
106
Tc
22
(104 Mev).
These fast ions pass through the sampIe both M
+
and M
-
are
produced.
In a spark source eIectrodes are made out of the
sampIe and a spark is generated to produce the ions. In a
spark source eIectrodes are made out of the sampIe and a
spark is generated to produce the ions.
In a photo ionization source the sampIe is irradiated
by intense Iight to produce ions.
23
MASS ANALYSER
The ions from the Mass anaIyzer ion source are repeIIed
by repeIIer eIectrodes which are acceIerated and injected
into mass anaIyzer. Here, the ions are separated
according to their (m/e). This principIe is iIIustrated by
Dempster's mass spectrometer.
In Dempster's mass spectrometer, positiveIy charged
ions entering from the ion source are acceIerated by
eIectrostatic fieId. A magnetic fieId H is appIied in a
perpendicuIar direction.
24
DEMPSTER'S MASS SPECTROMETER
Under the infIuence of this magnetic fieId, the ions
traveI in a circuIar path and faII on a coIIector after
traveIing 180
0
. The kinetic energy of an ion of charge e
acceIerated by a voItage, is equaI to V eV. That is,
1/2mv
2
=eV
V = VeIocity of the ions, m = mass, e = charge and v is
the (voItage) potentiaI appIied.
26
In a magnetic fieId, the ions experience a force HeV
such that it traveIs in a circuIar path of radius r.
By Newton's second Iaw,
F = ma. Hence a = F/m
a is aIso equaI to v
2
/r. Hence,
Hev/m = v
2
/r
H
2
e
2
= m
2
v
2
/r
2
But 1/2mv
2
= eV
Therefore H
2
e
2
= m
2
eV/r
2
m/e = H
2
r
2
/ 2V
27
If v is kept constant and H is varied (magnetic scanning)
ions with different m/e wiII reach the coIIector at different
vaIues of H. If H is kept constant and V is varied, the
process is caIIed voItage scanning.
28
Due to variations in the kinetic energy of the ions
entering the mass spectrometer from the ion source
the resoIution of Dempsters mass spectrometer is
Iimited. To overcome this probIem the ions are passed
through an eIectric fieId prior to the magnetic fieId.
The ions are focused and passed through a sIit into the
magnetic sector. This resuIts in high resoIution that
can distinguish m/e differences of the order of 0.01.
29
30
ION DETECTOR
The ion separated by the mass anaIyzer are measured
by the currents of the order 10A to 1aA they produce.
The ions pass through the coIIecting sIits and faII on
the coIIector eIectrode. The Iatter is shieIded thoroughIy
from stray ions. The recorder records peaks of aII sizes
and the scanned spectrum is recorded. It is possibIe to
repIace the coIIector eIectrode with a photographic pIate,
deveIop it and then measure the darkening at different
positions which is proportionaI to intensity of the
corresponding ions.
31
TIME OF FLIGHT MASS SPECTROMETERS
In a time of fIight mass spectrometer aII the ions
emerge from the eIectro static fieId with the same
energies. The ions with the Iargest mass wiII have the
Iowest veIocity, so they take the Iongest time to cover a
given distance. This is the principIe of a time of fIight
mass spectrometer.
32
SCHEMATIC DIAGRAM OF TIME OF FLIGHT
MASS SPECTROMETER
33
A voItage puIse on grid A extracts the ions from the source.
The ions are acceIerated by the potentiaI difference between
A and B and pass into a free fIight tube where there is no
fieId action on the ions. The ions are separated in time
according to m/e ratios an coIIected at D. Time difference
between successive peaks wiII be of the order of 0.1 sec.
k is a constant which depends on the Iength of free fIight.
m/e k t m/e t
34
QUADRUPLE MASS SPECTROMETER:
In a quadrupIe mass spectrometer four eIectrode
systems are used in which the opposite eIectrodes are
connected together. A constant voItage, u and a radio
frequency potentiaI, V are appIied between opposite
pairs of four paraIIeI rods. Ions are injected aIong x
direction and the spectrum is scanned by varying v
keeping the ratio u/v constant. These are reIativeIy
cheap instruments.
35
INTERPRETATION OF MASS SPECTRUM
Extensive Iibraries of mass spectrum are avaiIabIe and
it is possibIe to make aII the necessary concIusions by
matching the spectrum of the unknown sampIe with
the correct spectrum in the Iibrary with the heIp of a
computer. Otherwise, interpretation of a mass
spectrum depends on the though knowIedge of the
empiricaI facts reIevant to the case. In otherwords
interpretation of mass spectrum is a speciaIist's job.
36
NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY
1
NucIear magnetic resonance (NMR) spectroscopy is a
technique for determining structure of moIecuIes and
ions and for their quantization based on transitions
between the energy IeveIs of the atomic nucIeus under
certain conditions. The energy invoIved is in the radio
frequency range. OnIy those nucIei which have spin
give signaI in NMR. Even so, NMR is extremeIy usefuI
because the signaI given by a nucIeus is infIuenced by
its environment. In other words, the signaI from a
nucIeus gives information about its neighbouring atoms,
charge status etc. This often Ieads to determination of
compIete moIecuIar structure.
2
The nucIei of certain isotopes have an intrinsic spinning
motion around their axis. The spinning of a charged particIe
generates a magnetic moment aIong the axis of the spin.
3
If an externaI magnetic fieId is appIied, their spin can aIign
with or against the fieId. Each individuaI nucIeus spins
around its axis and the axis of the nucIear magnetic moment
so generated precesses about the Iine of force of the appIied
magnetic fieId, Iike a top as shown here.
4
The spinning motion of a nucIeus is quantized and is
associated with a spin quantum number I. The reIation
between the mass atomic number and spin quantum
number is shown in tabIe beIow:
5
Mass number,
(Protons +
Neutrons)
Atomic number
(no of Protons)
Z
No of
Neutrons
Spin
Quantum
no
I
ExampIes
Even Even Even 0
12
C,
16
O,
32
S
Odd Odd Even 1/2
3/2
1
H,
19
F,
31
P
11
B,
79
Br
Odd Even Odd 1/2
3/2
13
C
127
I
Even Odd Odd 1
2
H,
14
N
NucIei with both A and Z even have I = 0 and they do not give NMR signaIs.
6
For a nucIeus to be magnetic it must possess spin
anguIar momentum with a magnitude of .
The maximum observabIe vaIue of the spin anguIar
momentum is , ,where I is the spin quantum number
of the nucIeus and h is the PIank's constant. It generates a
magnetic moment () paraIIeI to the axis of spin. Like spin
moment, magnetic moment is aIso quantized. The magnetic
quantum number(m), has the vaIues -I, -I+1,.,0,..., I-1, I. The
ratio of the magnetic moment to the anguIar moment, , is
known as the gyromagnetic ratio. Different nucIei have
different .The maximum observabIe component of
magnetic moment, , has the vaIue .
1) (I I 2 / h
2 / I h
I 2 / / h I m
7
Those nucIei with I = 1/2 behave Iike charged, spinning
spheres and give weII resoIved spectra. Such nucIei
incIude
1
H,
13
C,
19
F and
31
P.
Among nucIei with I = 3/2,
7
Li,
11
B,
35
CI are important.
NucIei with integraI spins of I = 1 incIude
2
H and
14
N.NucIei
with spins greater than 1/2 behave Iike nonsphericaI
charged rotating bodies and show Iine broadening in NMR
spectra.
Many organic moIecuIes contain onIy C,H and O. Since
12
C and
16
O do not have nucIear magnetic moments onIy
the proton spectra are observed.
13
C has a Iow naturaI
abundance of 1.1% and is not observed in ordinary NMR.
8
The magnetic moment of a spinning nucIeus can assume
2I +1 orientations with respect to the externaI magnetic
fieId Ieading to 2I+1 discrete energy IeveIs. The energy
IeveIs can be caIcuIated using the equation,
E = -m I H
0
where I = spin quantum number, m is the magnetic
quantum number, is the magnetic moment of the
nucIeus, H
0
is the externaI (i.e., appIied) magnetic fieId
strength in gauss (G) and E is the energy corresponding
to that orientation (in vaIue).
The aIIowed vaIues of m are I, (I-1), ..., 0, ...(-I+1), -I.
Thus a nucIeus with spin 1/2 has 2 orientations, with spin
1 has 3 orientations; and so on.
9
NUCLEAR ORIENTATION AND ENERGY
LEVELS OF NUCLEI IN A MAGNETIC FIELD
10
Transitions between the energy IeveIs produced by the
appIication of a magnetic fieId can occur according to
the seIection ruIe m = 1. The resonance frequency,
that makes the transition possibIe is given by,
Keeping the appIied magnetic fieId H
0
constant, if an
increasing radio frequency (rf) current is passed through
a coiI in the YZ pIane, the rf frequency creates an
aIternating magnetic fieId(H
1
), in the x direction. When H
1
equaIs the resonance frequency , energy is absorbed by
the spinning nucIeus, fIipping the spin direction such that
its magnetic moment precesses against the appIied fieId.
This is known as Larmor frequency.
0

I
H
h
0
0

E
0

11
There is a Iinear reIationship between the resonance
frequency and the appIied magnetic fieId H
0
. Therefore,
either H
0
can be kept constant and sweep radio frequency
(rf) or keep a constant rf and vary the appIied magnetic
fieId H
0
.
Magnetic fieId strength can be expressed in units of
Gauss (G) or TesIa (T). 1T = 10,000 G
12
For a proton = 1.41 x 10
-30
JG
-1
or 2.7927 nucIear
magnetons. If a magnetic fieId of 14092 G is appIied,
Thus, the resonance frequency of a proton in a
magnetic fieId of 14,092 G wouId be 60 MHz.
In NMR the strength of the signaI is approximateIy
equaI to the square of the magnetic fieId appIied.
Strong magnetic fieIds can be produced using super
conductors.
sec 60x10 sec
(0.5) sec) 10 626 . 6 (
G) (14,092 ) G J 10 (1.41

h
E

1 - 6 1 -
34
-1 30 -
0

13
14
When there are two aIIowed energy IeveIs the
distribution of a popuIation of nucIei at equiIibrium
foIIows BoItzmann equation:
n
upper
n
Iower
where K is the BoItzmann constant and T is the
absoIute temperature.
= e
- H
0
/KT
15
For a proton at 14.09 kG appIied magnetic fieId
n
upper
n
Iower
. Therefore it is easy to saturate the
system. That is, after a very short time, there wiII be no
signaI because the number of nucIei absorbing rf energy
wiII be equaI to the number of nucIei reIeasing the same
rf. Therefore, reIaxation processes that aIIow nucIei in
higher energy state to return to the Iower state (by
different ways) are important for the reIaxation back to
the Iower energy state. Therefore a constant absorption
signaI can be observed.
16
Two types of reIaxation processes occur. One, spin-Iattice
or IongitudinaI reIaxation by which the nucIei with higher
energy transfers its energy to other nucIei to increase
their transIationaI or rotationaI energy, for exampIe. This
process is associated with a time constant, T
1
, which is
the time required for (the BoItzmann distribution) the
ratio n
upper
/ n
Iower
to reach 1/2 of its initiaI vaIue in
the presence of H
0
.
17
The second type of reIaxation is the spin-spin (or
transverse) reIaxation. In this process, the nucIei
exchange spins with neighboring nucIei by interaction
of their magnetic moments. AIthough no energy is Iost
by this mechanism, the precessing nucIei Ioose phase
coherence. Some precess faster and some precess
sIower. The net magnetization in the XY pIane faIIs
towards zero. The time constant associated with this
process is T
2
.
18
For soIids and viscous Iiquids T
1
is of the order of hours
and for Iiquids and diIute soIutions T
1
is in the range
0.01-100 sec. In generaI T
2
T
1
.
The width of the absorption Iine is reIated to T
1
by the
equation,
where is the Iine width at haIf height in hertz. If
T
1
is 1sec, the Iine width at haIf height in hertz wouId be 1.
1
1,2
T
1

2 , 1

19
The conventionaI NMR spectrometers scan the spectrum
sIowIy to avoid passing very narrow Iines too fast. Most
of the time is spent on recording the background and
onIy a smaII amount of time is utiIized for recording the
peaks which contain aII the information one Iooks for.
This Ieads to Iow efficiency and Iow sensitivity.
Time required for a scan by conventionaI method is
given by /r,
where is the range of frequencies required to be
scanned and r is the resoIution desired.
20
For a
13
C NMR at 25 MHz and a typicaI of 5 kHz and
the Iine widths of about 1Hz, the scan rate has to be 1
Hz sec
-1
and the totaI time required is 1 h 23 minutes.
If the spectrum is divided into a Iarge number(N) of
smaII frequency intervaIs and if aII these frequencies
are appIied simuItaneousIy the spectrum can be
obtained much quickIy. If N is equaI to the bandwidth
of the signaI, S/N ratio improves by a factor of (N)
1/2
.
This is known as FeIgett's advantage. This is achieved
in Fourier Transform (FT) NMR. FeIgett's advantage for
a proton is about 30 and for
13
C, it is about 100.
21
In FTNMR a strong rf puIse is appIied to the sampIe
in a short time of 1-100 secs. This is appIied by means
of a coiI pIaced paraIIeI to X-axis of the spectrometer.
The puIse contains a wide band of frequencies on
either side of the center. Due to this aII the magnetic
nucIei are excited simuItaneousIy. After the puIse, the
precessing magnets revert back to their originaI state
inducing a sinusoidaI voItage in a coiI surrounding the
sampIe. This is the sum of aII signaIs. After Fourier
transformation, the spectrum appears simiIar to
conventionaI spectrum.
22
NucIear magnetic resonance frequencies are to a smaII
degree dependent on the moIecuIar environment of the
nucIeus. Since surrounding eIectrons shieId the nucIeus,
the effective magnetic fieId experienced by the nucIeus
is sIightIy different from the appIied fieId. EIectronic
shieIding resuIts from an induced circuIation of eIectrons
about the nucIeus. These circuIations are induced by the
appIied fieId and are in a direction perpendicuIar to the
appIied fieId. They produce a magnetic fieId opposing the
appIied fieId and proportionaI to the magnitude of the
appIied fieId.
The effective magnetic fieId, H
eff
= H
0
- H
0
.
where H
0
is the induced magnetic fieId. The separations
of resonance frequencies of nucIei in different structuraI
environments from some arbitrary standard is known as
chemicaI shift.
23
NMR spectra in which the width of the resonance Iine is
as Iarge as or Iarger than the resonance shifts caused by
different chemicaI environments are known as wide-Iine
NMR. These can give information regarding concentration
and physicaI environment of nucIei but not their chemicaI
environments. Wide Iine NMR provides a rapid and
nondestructive method of quantitative anaIysis.
For exampIe, proton contents of fats and oiIs can be
measured. Moisture content in a variety of sampIes can be
determined by wide-Iine NMR. FIuorine in fIuorocarbons
can be determined. The width of the absorption Iine is
reIated to motionaI freedom of the nucIeus in the Iattice.
This gives vaIuabIe information to poIymer chemists and
soIid-state physicists.
24
CONTINUOUS-WAVE NMR SPECTROMETERS
Continuous-wave NMR instruments consist of six basic
units:
A powerfuI magnet.
Two or more rf channeIs. One serves to stabiIize the
magnetic fieId or radio frequency and another provides
irradiating energy. A third rf coiI may be used for
decoupIing nucIei.
A sampIe probe containing coiIs for coupIing the sampIe
with the rf fieId.
25
A detector to process the NMR signaIs.
A sweep generator for either magnetic fieId or for
radio frequency fieId.
A recorder to dispIay the spectrum.
26
SCHEMATICS OF CONTINUOUS-WAVE NMR
SPECTROMETERS
27
The magnet shouId give a high fieId strength which is
homogenous and stabIe. The stronger the fieId, the
better the separation of the absorption Iines. AIso,
muItipIet overIapping decreases with increasing fieId
strength.
In a stronger fieId the separation of energy IeveIs of
nucIei is greater and the BoItzmann distribution favours
the Iower IeveI. Therefore sensitivity aIso increases. To
ensure homogeneity of magnetic fieId two Iarge poIe
pieces made of a homogenous metaI are used.
28
The poIe faces are poIished. The gap between the
poIes is kept narrow. SIim coiIs are used for
correcting any inhomogeneity. Permanent magnets
are cheaper than eIectromagnets but require eIaborate
shieIding and shouId be thermostated to 0.001
0
C.
EIectromagnets require eIaborate power suppIy and
cooIing systems but they can be operated at different
fieId strengths. CommerciaI NMR spectrometers
operate at 14.09, 21.14 or 23.49 kG. Using super
conductivity technoIogy 51.7, 70.5, 93.5 or 117.4 kG
fieIds can be produced providing high resoIution NMR.
29
THE PROBE UNIT
The probe unit is the sensing eIement of the
spectrometer. It is inserted between the magnetic
poIes by an adjustabIe probe hoIder. The probe hoIder
houses the sampIe hoIder, the rf transmitters, output
attenuator, receiver and a phase-sensitive detector.
The sampIe hoIder is a thin waIIed gIass tube of 5mm
outer diameter. To average minute inhomogeneities
the sampIe hoIder is rotated at 1200 to 2400 rpm. The
sampIe is fiIIed to get a Iength / diameter ratio of 5.
30
A few micrograms to a few miIIigrams of the sampIe is
dissoIved in a soIvent Iike CCI
4
, CS
2
or a compIeteIy
deuteriated chIoroform, acetone or benzene. The soIvent
shouId not contain hydrogen. The magnetic resonance
response of the deuterium nucIei is used to Iock the ratio
of the magnetic fiIed and frequency of the instrument over
Iong periods of time. SingIe coiI probes as weII as duaI
coiI probes are avaiIabIe. Tetra methyI siIane (TMS) is
traditionaIIy used as an internaI standard.
31
TYPES OF CONTINUOUS WAVE NMR
SPECTROMETERS
MinimaI type NMR spectrometers are reIativeIy cheap and
suitabIe for proton NMR spectraI measurements.
MuItipurpose NMR spectrometers are more sophisticated
and versatiIe. They provide high precision and they are
used in research.
Wide-Iine NMR instruments have a permanent or a
Iight-weight eIectromagnet with Iarge sampIe tubes
(15 to 18mm outer diameter). The sampIe temperature can
be varied from -170 to +200
0
C.
32
FOURIER TRANSFORM NMR SPECTROMETER
A Fourier transform NMR spectrometer is simiIar to the
continuous wave NMR spectrometer except that it has
a computer controIIed puIse generator and a digitaI
computer for signaI processing and presentation of
spectra. Operator skiII requirements are much
reduced.
33
SCHEMATICS OF FTNMR
34
MAGIC ANGLE SPINNING
In powdered soIid sampIes, moIecuIes are oriented in
aII possibIe directions. This resuIts in a broadening of
the NMR Iines. The shieIding of any particuIar nucIeus
depends upon the eIectronic environment and the
orientation of the moIecuIes in which it is present.
This is known as ChemicaI Shift Anisotropy.
This can be overcome to a Iarge extent by rotating the
sampIe very rapidIy (speeds > 2 kHz) about an axis
oriented at an angIe of approximateIy 54.7
0
, the magic
angIe, with respect to the appIied magnetic fieId. The
averaging that occurs is simiIar to tumbIing in Iiquids.
The angIe is a property of the IocaI fieIds that eIectrons
exert on the nucIei.
35
Important parameters NMR spectra provide are
chemicaI shifts, coupIing constants, spin-Iattice (T
1
)
and spin-spin (T
2
) reIaxation times.
The same type of nucIeus in different chemicaI
environments experience different shieIding from the
appIied fieId depending on the distribution of eIectronic
charge in its surroundings. If the externaI fieId H
0
is heId
constant, different shieIding effects cause sIightIy
different resonance frequencies.
36
The magnitude of effective fieId feIt by each group of
nucIei is given by,
H
eff
= H
0
- H
0
where is a shieIding constant which can be positive
or negative. The more the fieId induced by the
circuIating eIectrons shieIding the nucIeus (opposes the
appIied fieId), the higher must be the appIied fieId to
achieve resonance.
37
The vaIue of the shieIding constant depends on severaI
factors, among which are hybridization and eIectro
negativity of the groups attached to the atom to which
the nucIeus beIongs. ShieIding effects rareIy extends
beyond one bond Iength.
To express the position of the resonances independent
of the strength of the appIied fieId the resonance of a
reference compound is required. For proton spectra in
nonaqueous media, the reference materiaI is
tetramethyI siIane. TMS gives a singIe sharp signaI
due to 12 equivaIent protons and this is taken as 0.0 on
the chemicaI shift () scaIe.
38
The magnitude of the chemicaI shift is expressed as
parts per miIIion:
where H
ref
and H
sampIe
are the positions of the absorption
Iines for the reference and the sampIe, respectiveIy
expressed in Gauss and V ref and V sampIe are the
corresponding frequencies expressed in hertz. A positive
represents a greater degree of shieIding than in the
reference.
6
reference
reference sample 6 -
reference
sample ref
10
-
10
H
H - H

39
For other nucIei, recommended reference materiaIs are:
CS
2
or TMS for
13
C
CCI
3
F for
19
F
NH
3
Iiquid for
14
N and
15
N
TMS for
29
Si
85% Orthophosphoric acid for
31
P
40
Proton resonances from C-H bonds are found in the range
= 0.9 to 1.5 when onIy aIiphatic groups are substitutents.
CH
3
protons generaIIy show up sIightIy down fieId in that
order. If there is an adjacent unsaturated bond the CH
3
proton resonance shifts to = 1.6 - 2.7.
An adjacent oxygen atom markedIy shifts proton signaIs
downfieId to = 3.2 to 3.4 for aIiphatic entities and to
= 3.6 - 3.9 for aryI-O-CH entities.
When a doubIe or a tripIe bond is present in a moIecuIe the
eIectrons in these bonds can circuIate onIy in certain
preferred directions. Figure shows shieIding (+) and
deshieIding (-) zones in the neighborhood of tripIe, doubIe
and singIe bonds to carbon.
41
SHIELDING MECHANISMS
42
In C=C and C=O doubIe bonds, the deshieIding zone
extends aIong the bond direction. C-C bonds aIso show
some deshieIding in this direction. The deshieIding
of a proton depends on the Iatter's distance from the bond
and aIso on its orientation with respect to that bond,
Aromatic rings have a strong anisotropic effect. The
deIocaIized eIectrons of an aromatic ring circuIate in
two doughnut-shaped orbits on each side of the ring under
the infIuence of the appIied magnetic fieId, H
0
.
43
This circuIation resuIts in a magnetic fieId that opposes
H
0
in a cone-shaped region of excess shieIding that
extends aIong the perpendicuIar to the ring pIane but it
reinforces H
0
in a zone of deshieIding from the edge of
the ring.Thus, in aromatic compounds, protons which are
usuaIIy found in the deshieIding zone appear at much
Iower fieIds ( = 6 to 7 ) than oIefinic protons ( = 5 to 6).
In acetyIenes, the eIectron current circuIates in such a
way that the shieIding zone extends aIong the bond
direction and acetyIenic protons appear at higher
fieIds ( = 1.6 to 3.0).
44
CHEMICAL SHIFT OF SOME COMPOUNDS
45
CHEMICAL SHIFT OF SOME COMPOUNDS.
46
SPIN-SPIN COUPLING
NucIei in proximity interact with each other causing a
spIitting of resonance Iines into muItipIets. This is
caIIed spin-spin coupIing or J coupIing. This is due to
interaction of magnetic moments of the nucIei through
the magnetic properties of the eIectrons in the
intervening bonds. The strength of the coupIing is
denoted by J which is equaI to the spacing of the
muItipIets in hertz. Proton - proton coupIings in
aIiphatic organic compounds are normaIIy transmitted
through onIy two or three bonds.
47
PROTON SPIN-SPIN COUPLING CONSTANTS
48
In doubIe bond straight chain systems coupIing can be
observed over severaI bond Iengths. In aromatic rings,
coupIings of protons in ortho positions are 7- 9 Hz, meta
2-3 Hz and para 0.5-1.0 Hz.
CoupIing aIso depends on geometry. AxiaI-axiaI protons
are strongIy coupIed but axiaI - equatoriaI and equatoriaI-
equatoriaI protons are coupIed moderateIy. It has been
shown that J
trans
J
eis
The number of Iines in a muItipIet is given by 2n + 1
where n is the number of nucIei invoIved. For protons,
this becomes n + 1 Iines.
2
49
In a muItipIet, the totaI intensity is proportionaI to the
number of nucIei invoIved and the reIative intensities
of the individuaI peaks foIIow the coefficients of
binomiaI expansion. Thus, one neighboring proton
spIits the observed resonance into a doubIet (1:1), two
produce a tripIet (1:2:1), three a quartet (1:3:3:1), four a
quintet (1:4:6:4:1) and so on.
50
The magnitude of J is independent of the fieId strength.
Other nucIei with spin 1/2., i.e.,
19
F and
31
P interact
with protons and cause spin-spin spIitting. J is usuaIIy
Iarger than for proton-proton coupIing.
13
C proton
coupIing can be noticed.
When a proton is coupIed to a nucIeus that has a
quadrupoIe moment, spin-Iattice reIaxation becomes so
efficient (T
1
is reduced) that the spin-spin interaction
with proton is greatIy or compIeteIy decoupIed.
CoupIing of protons with chIorine, bromine or iodine is
thus not observed. In case of
14
N, the decoupIing is
partiaI, so
14
N-
1
H protons give a broad peak.
51
DOUBLE RESONANCE (SPIN DECOUPLING)
To remove the coupIing of spins an additionaI rf fieId, ,
perpendicuIar to is appIied. is the resonance
frequency of the nucIei being observed and is that
for the nucIei causing spin-spin spIitting. Then the
muItipIets coIIapse into a singIe peak of intensity equaI
to the totaI intensity of the muItipIet. This increases
the sensitivity of the measurement. It is a common
practice to decoupIe protons for observing
13
C spectra
because
13
C has a Iow abundance. Hence higher sensitivity
is desirabIe.
2

52
NUCLEAR OVERHAUSER EFFECT (NOE)
The nucIear overhauser effect is observed when the
signaI of one nucIeus (
1
H) is saturated and that of
another nucIeus (
13
C) is not spin coupIed. DecoupIing
takes pIace due to intra-moIecuIar dipoIe-dipoIe
reIaxation. The intensity of the signaI (
13
C) wiII be more
than the totaI intensities of the muItipIets that wouId have
shown up if there was no decoupIing. This additionaI gain
in intensity is the overhauser effect. This arises because
saturation of one nucIeus (
1
H) causes a change in the
popuIation of the nucIear energy IeveIs of the other
nucIeus (
13
C).
53
MAGNETIC RESONANCE IMAGING (MRI)
Proton rich soft tissues of the human body can be
imaged using nucIear resonance to compIement the x-ray
images of the bones. UnIike x-ray there is no heaIth risk
in MRI because the energy invoIved is Iow. The image is
produced by appIying gradient magnetic fieId when protons
in different Iocations resonate at different frequencies and
then combining aII the signaIs to reconstruct an image.
54