142

3.4 Infrared spectroscopy

3.4.1 Origin of IR absorption
Infrared spectroscopy is a technique which uses EMR in the IR
region to measures the bond vibration frequencies in a molecule
and is used to determine the functional group.

There are three IR regions (near, mid and far).

Table 3C.1 IR spectra regions

143
 Absorption of IR radiation by molecule
 Molecules are made up of atoms linked by chemical bonds.

 Thus, absorption of IR radiation cause the movement of atoms and the

chemical bonds like spring and balls (vibration).

 This causes vibrational or rotational

energy transitions.

 However, IR radiation is not energetic

enough to bring about electronic
transitions. 144
Selection rule for the absorption of IR radiation by molecules
 To absorb IR radiation, a molecule must undergo a net change in dipole
moment as it vibrates or rotates.

 As a molecule vibrates, a regular fluctuation in its dipole moment occurs,

and a field is established that can interact with alternating electric field of
the radiation.
145
 If the frequency of the radiation exactly matches a natural vibrational
frequency of the molecule, absorption of the radiation takes place.

natural frequency of vibration = frequency of the incident radiation

∆E = hv

 However, molecules with no net change in dipole moment cannot absorb

IR radiation and called IR inactive.

146
 There infrared spectrum have two fundamental region.
(a) Functional group region (4000 cm-1 - 1250 cm-1)
 dependent only on the functional group that absorbs
(b) Fingerprint region (1250 cm-1 - 600 cm-1).
 dependent on the complete molecular structure

147
 The IR spectrum is plot is % transmittance against wavenumber

148
Instrument
Design

149
 Types of Molecular Vibrations
 The positions of atoms in a molecules are not fixed; they are subject to a
number of different vibrations.

 Vibrations fall into the two main categories: stretching and bending.

 Stretching: Change in inter-atomic distance along bond axis.

Instrument
Design

Symmetrical Asymmetrical
stretching stretching
150
 Bending: Change in angle between two bonds. There are four types of
bend.

In-plane rocking In-plane scissoring Out-of-plane wagging Out-of-plane twisting

151
 Theoretical number of fundamental modes of vibration
 It is possible to deduce the number & kinds of vibrations in simple
diatomic and triatomic molecules & whether vibrations will lead to
absorption.

 For a molecule with N atoms, a total of 3N coordinates [(three

coordinates (X, Y and Z)] is required, and the molecule is said to have
3N degrees of freedom of motion.
Linear Molecules: (3N - 5) degrees of freedom

Non-Linear molecules: (3N - 6) degrees of freedom

 In general, three of these degrees are translation, while three describe

rotations.

152
 In a non-linear molecule, 3 of these degrees of freedom are rotational, 3
are translational and the remainder is fundamental vibrations.

 In a linear molecule, there are 3 translational degrees of freedom and 2

are rotational.

 This is because in a linear molecule, all of the atoms lie on a single

straight line and hence, rotation about the bond axis is not possible.

 The total degrees of freedom for

H2O is 3(3)-6 = 9-6 = 3. 3760 cm-1 3650 cm-1 1595 cm-1

153
Vibrational Frequency
 In diatomic molecule with two masses m1 and m2 connected by a
massless spring the stretching frequency of a bond can be approximated
by Hooke’s Law.

Figure 3D-1: Potential-energy diagrams. (a) harmonic oscillator. (b) Curve 1,

harmonic oscillator; curve 2, anharmonic motion
154
 Applying the Hooke’s Law the natural frequency, vm of oscillation can be
estimated using

 The exact wavenumber at which a given vibration occurs is determined by

or depends on:
 strengths of the bonds (K)
 the mass of the attached body

substituting the reduced mass μ for the single mass m

155
 Quantum Treatment of Vibrations
 Using the harmonic oscillator and wave equations of quantum
mechanics, the energy can be written as

where h is Planck's constant, and v is the vibrational quantum

number, which can take only positive integer values (including zero).

where vm is the vibrational frequency of the classical model.

156
 Because v in above equations can assume only whole numbers,
that is

 At room temperature, the majority of molecules are in the ground

state v = 0; thus,

 Promotion to the first excited state v = 1 with energy

requires radiation of energy

157
 The frequency of radiation v that will bring about this change is
identical to the classical vibrational frequency of the bond.

Or

 If we wish to express the radiation in wavenumbers, we substitute

158
 k is the force constant (N/m), c (cm/s), and µ is the reduced mass (kg).

 Generally, k for most single bonds ranges average value of 5 x 102 N/m
and double - 1 X 103 and triple bonds-1.5 X 103 N/m.

 Above equation can be used to estimate the wavenumber of the

fundamental absorption band for a variety of bond types.

159
Example:
Calculate the approximate wavenumber and wavelength of the
fundamental absorption due to the stretching vibration of a carbonyl
group C=O.

160
and the reduced mass µ is given by

 As noted earlier, the force constant for the typical double bond is about
1 x 103 N/m. Substituting this value and µ into the equation gives

The carbonyl stretching band is found experimentally to be in the region

of 1600 to 1800 cm-1.
161
 3.4.2 IR Instrumentation
There are three types of instruments for IR absorption measurements

(a) Dispersive spectrophotometers with a grating monochromator.,

(b) Fourier transform spectrometers employing an interferometer

(c) Nondispersive photometers using a filter or an absorbing gas that

are used for analysis of atmospheric gases at specific wavelengths

162
(a) Dispersive IR spectrophotometers
 It is a double-beam like spectrophotometer, recording instruments,
which use reflection gratings for dispersing radiation.

 But, in IR instrument the sample and reference compartments are

always located between the source and the monochromator.

 This arrangement is used because IR radiation is not sufficiently

energetic to cause photochemical decomposition of the sample.

 It incorporate a low-frequency chopper that permits the detector to

discriminate between the signal from the source and signals from
extraneous radiation, such as IR emission.

163
 The grating separates the wavelengths of light in the spectral range and
directs each wavelength individually through a slit to the detector.

 Each wavelength is measured one at a time, with the slit monitoring the
spectral bandwidth and the grating moving to select the wavelength being
measured.

Figure 3D-2 Diagram classical dispersive IR spectrophotometer.

164
(b) Fourier transform IR(FT-IR) spectrometers
 FTIR instruments are based on the Michelson interferometer, which
allows all the frequencies to reach the detector at once.

 In the 1870’s Michelson was measuring light and its speed with great
precision and reported the speed of light with the greatest precision to
be 299,940 km/s and for this he was awarded the Nobel Prize in 1907.

Figure 3D-3 Diagram FT-IR spectrophotometer 165

Michelson Interferometer (MI)
 MI, which is the core of FTIR spectrometers, is used to split one beam of
light into two so that the paths of the two beams are different.

 Then the MI recombines the two beams and conducts them into the
detector where the difference of the intensity of these two beams are
measured as a function of the difference of the paths.

Figure 3D-4 Schematic of the Michelson Interferometer.

166
 The two light rays with a common source combine at the half-silvered
mirror (beamsplitter) to reach the detector. They may either

 Interfere constructively (strengthening in intensity) if their light waves

arrive in phase

 Interfere destructively (weakening in intensity) if they arrive out of phase,

depending on the exact distances between the three mirrors.

 Then, the recombined beam passes through the sample.

 The sample absorbs all the different wavelengths characteristic of its

spectrum, and this subtracts specific wavelengths from the interferogram.

 The detector now reports variation in energy vs time for all wavelengths
simultaneously.

167
 A plot of the signal versus mirror displacement is the interferogram.

 The interferogram contains information about all the frequencies present.

 The spectrum, intensity vs wavenumber, is the FT of the interferogram.

 It can be calculated with a computer from the signal versus mirror

displacement.

168
 This is the "raw data" which can be Fourier transformed to get the
actual spectrum.

169
170
 Procedures of data acquisition using FTIR instrument
1. Reference scan
 First reference interferogram is obtained by scanning a reference
empty sample compartment (usually air) .
 Then, the reference spectrum is calculated by co-adding the data,
and storing the results in the memory of the instrument computer
(usually after transforming it to the spectrum).
2. Sample scans
 A sample is then inserted in the radiation path (in the sample
compartment) and the sample spectrum is obtained.
 The ratio of sample and reference spectral data is then computed to
give the transmittance at various frequencies.
 From this ratio, the absorbance is calculated as a function of
wavenumber. 171
 Advantages of FTIR instrument
 Have higher signal-to-noise ratio for a given scan-time → because
information from all wavelengths is collected simultaneously.

 It is characterized by high resolutions and highly accurate and

reproducible frequency determinations.

 Interferometer provide high throughput since it is determined only by the

diameter of the collimated beam coming from the source.

 Allows very good reproducibility of the wavelength or wavenumbers

because of the use a of small HeNe laser (not as a source).

172
 IR SOURCES AND TRANSDUCERS
(1) Light source
 IR sources consist of an inert solid that is heated electrically to a
temperature between 1500 and 2200 K.
 This heated material will then emit IR radiation. The following are
some of the source.

(a) Nernst Glower:

 It is composed of rare earth oxides formed into a cylinder having a
diameter of 1 to 3 mm and a length of 2 to 5 cm.
 Its temperature increases to between 1200 K and 2200 K.
 It operates at approximately ~2200 K

 A ceramic of zirconium oxide - yitrium oxide was used as the glowing

rod. 173
(b) Globar
 It is a ceramic rod, usually silicon carbide a composite material,
electrically heated to more than 1000 K.

 Globar sources for FTIR must be temperature controlled for high

stability.

(c) The Tungsten Filament Lamp

 A convenient for the near-IR region of 4000-12,800 cm-1.

(d) Semiconductor IR Laser Sources

 Used in in the near and mid-IR regions
 A tunable diode laser spectrometer in the 2.78 μm region is used to
detect carbon, hydrogen, and oxygen in the Martian environment.
 A quantum cascade tunable laser is used to detect methane by
scanning across several of its rotational lines in the 3.3 μm region. 174
(e) The Mercury Arc
 It is quartz-jacketed tube containing mercury vapor.
 Used for far-IR region of the spectrum (1-50 µm).

(f) The Carbon Dioxide Laser Source

 Produce band of radiation in the range of 900 to 1100 cm-1
 Used for monitoring the concentrations of certain atmospheric
pollutants and absorbing species in aqueous solutions.

 Very bright, several orders of magnitude brighter than other

sources, but not flexible.

 Thus, this source is useful for quantitative determination of a

number of important species such as ammonia, butadiene,
benzene, ethanol, nitrogen dioxide, and trichloroethylene
175
175
(2) Sample cells and sampling of substance
 IR are used for solid, liquid and gas.
 Material containing sample must be transperent to IR region.
 Sample cell constructed from rock salt.
 Sample must be pure and free from water.

(a) Gas samples

The dried gases introduced via a stop cork
The gas sample is introduced into the gas cell
made up of glass or metal cylinder
The end walls of the gas cell are made up of. NaCl windows
 Long path length (10cm – 10m).
176
(b) Liquid samples
Various cell like demountable cell and cavity cell
Made up of NaCl, KBr or thallium bromide.
Long path length (0.015 – 1mm).

Instrument
Design

177
(c) Solid samples
 Solid dissolved in solvent
 a convenient way of obtaining IR spectra is on solutions
prepared to contain a known concentration of sample.

 solvents should be transparent over significant regions in the IR.

 Water and the alcohols are difficult to use as solvents in IR

Instrument
Design
spectrometry.

178
 Most organic compounds exhibit numerous absorption bands throughout
the mid-IR region, and hence finding a solvent that does not have
overlapping bands is often impossible.

 On the other hand the solid sample must be ground until its particle size
is much less than the wavelength of the radiation to avoid the effects of
scattered radiation.

 There are some techniques for handling solid samples for handling solid
samples

 Pellet techniques

 Mull techniques

 Thin film

179
(a) Pellet Technique (Disk Method)
• The small amount of finally ground solid sample is mixed with 100 times
its weight of powdered KBr.

• The mixture is then pressed at 10,000 to 15,000 pound/in2 to yield a

transparent disk.

• The disk is then held in the instrument beam for spectroscopic

examination.

• Although KBr is the most frequently used pelleting salt, materials such
as CsI and CsBr are sometimes used.

• Cesium iodide has greater transparency at low frequencies than KBr

180
(b) Mull technique
• Used for solids samples which are not soluble in an IR-transparent
solvent or are not conveniently pelleted in KBr.

• The solid sample is prepared by dispersing the analyte in a

mineral oil or a fluorinated hydrocarbon mull (nujol) to form a paste.

• This paste is then sandwiched between two salt plates and used for
spectral measurement.

• The sample must be ground to particle size lower than 0.4–0.5 μm

(must be about one-fifth of the shortest wavelength to be used).

181
 Mull is formed grinding a 2.5 mg of the sample & 2-3 drops of nujol oil.

 Grinding should result in an even, smooth, glossy sample in the mortar.

 Nujol (hydrocarbon oil) has absorption at 2915,1462,1376 and 719 cm-1.

182
(3) Detectors
 There are three kinds of IR transducers
Thermal detector
Pyroelectric detector (specialized “thermal detector”).
Photoconducting detector (transducer).

(a) Thermal transducer

 It is used in older dispersive instruments but are too slow to be used
in FTIR spectrometers.

 There are two types of thermal detector.

 Thermocouple
 Bolometers
183
Thermocouple
 It consists of a pair of junctions formed when two pieces of a metal
such as bismuth are fused to each end of a dissimilar metal such as
antimony.

 The two fine wires are welded in blackened gold foil (to improve its
heat-absorbing capacity) and sealed in an evacuated chamber with a
window that is transparent to IR radiation (not glass o quartz).

 One welded joint (cold junction) is kept at constant temp.

 The other welded joint (hot junction) is exposed to radiation.

 A potential difference between the two junctions varies with their

difference in temperature.

184
Instrument
Design

Figure 3D-5 : Schematic diagram of a thermocouple. The “hot junction” is

exposed to the infrared radiation. The “cold junction” is insulated from it.
The current is proportional to T1-T2.
185
(2) Photoconducting Detectors
 thin film of semiconductor (ex. PbS, HgTe-CdTe) on a nonconducting
glass surface and sealed in a vacuum.
 Absorption of radiation by these materials promotes nonconducting
valence electrons to a higher energy-conducting state, thus
decreasing the electrical resistance of the semiconductor.

 PbS photoconductor used near-IR region

 HgTe-CdTe photoconductor for mid- and far-IR region.

hn vacuum

semiconductor
Transparent
glass to IR
186
(3) Pyroelectric Detectors
 constructed from single crystalline wafers of pyroelectric materials,
which are insulators with very special thermal and electrical properties.
 Pyroelectric substances, in contrast, retain a strong temperature-
dependent polarization after removal of the field.
 Thus, by sandwiching the pyroelectric crystal between two electrodes,
one of which is IR transparent, a temperature-dependent capacitor is
produced.
 Pyroelectric transducers exhibit response times that are fast enough to
allow them to track the changes in the time domain signal from an
interferometer.
 For this reason, many FTIR spectrometers for the mid-IR region use this
type of transducer.

187
 3.4.3 Applications of Infrared Spectrometry
 Infrared spectroscopy is widely used in industry as well as in research.

 Some of the major applications of IR spectroscopy are as follows

(a) Qualitative analysis

 Identification of unknown samples by matching the

absorption spectra with that of known compounds

 Identification of functional groups present in a sample

(classification of unknowns)

188
 Different types of groups of atoms (C-H, O-H, N-H, etc…) absorb
infrared radiation at different characteristic wavenumbers.

 No two molecules will give exactly the same IR spectrum (except

enantiomers.

 First is determination of the functional groups present by examining the

group frequency region (3600 cm-1 - 1250 cm-1)

 Second is comparison of the spectrum of the unknown with the spectra

of pure compounds (i.e fingerprint region (1200 -600 cm-1 ).

 Spectral matching can be done by computer software and library

spectra

189
(a) Group Frequencies
 Group frequencies for several functional groups fall in the range of 3600-
1250 cm-1 & a few fall in the fingerprint region, such as C-O-C & C-Cl
stretching vibration at 1200 cm-1 & 700 to 800 cm-1 respectively.

 In general, the IR spectrum can be split into four regions for interpretation

190
Figure 3D-7 The group frequency region of the mid-IR (3600–1250 cm-1) is used to
identify common functional groups. The fingerprint region (~1200–600 cm-1) is used
to identify compounds.
191
 Factors Influencing Group Frequencies
 There are various factors that contribute to the position, intensity and
appearance of IR bands
a) Symmetry
b) Coupling
c) Resonance
d) Hydrogen Bonding
e) Ring Strain
f) Electronic Effects

192
(a) Symmetry
 For a particular vibration to be IR active there must be a change in dipole
moment during the course of the particular vibration.

 Example: the carbonyl vibration causes a large shift in dipole moment,

and therefore an intense band on the IR spectrum.

+ - vibration + -
C O C O

 For a symmetrical acetylene, it is clear that there is no permanent dipole

at any point in the vibration of the C≡C bond. No IR band appears on
the spectrum.
vibration
C C C C

193
(b) Coupling
 In a multi-atomic molecule, coupling vibration for functional groups occur
for adjoining bonds and absent in a molecule with more than two bonds
separated atoms.

 For example, the calculated and observed ̅ for most C=C bonds is
around 1650 cm-1
 In allene, however, coupling of the two C=C systems gives two IR bands
at 1960 and 1070 cm-1 due to coupling.

H
H
C C C
H
H
194
(c) Hydrogen Bonding
 Intramolecular H-bonding with carbonyl compounds can serve to lower
the absorption frequency.
CH3
CH3
O
1680 cm-1 O
1724 cm-1
O
O
H
O

 Hydrogen bonding weakens the O−H bond; its absorption frequency

then will be lower.

195
 Gas phase Neat liquid

 The spectra of alcohols are characterized by an absorption band at 3300

cm-1, which corresponds to the O-H stretching vibration.

 The exact position of this band depends to a large extent upon the
degree of hydrogen bonding or association to which the hydroxyl group
is subject.

 Upon association, the energy and force constant of the O-H bond
decreases, and the absorption band is therefore shifted to a lower
frequency by about 200 cm-1.
196
 120
Vapor phase spectrum(135 °C)
100

80
% Transmittance

liquid film
60

40

20

0
4000 3500 3000 2500 2000 1500 1000
Wavenumbers, cm-1

Figure 3D.9 The liquid and vapor spectra of phenol. OH

197
(d) Ring Strain
 Certain functional group
frequencies can be shifted if
one of the atoms hybridization
is affected by the constraints of
bond angle in ring systems.

 Consider the C=O band for the

following cycloalkanones:
O
O

1775 cm-1 1750 cm-1

O O

1750 cm-1 1715 cm-1 198

(e) Electronic Effects
Inductive
 The presence of a halogen on the α-carbon of a ketone raises the
observed frequency for the π-bond.
O

C

Resonance 
X


 Contribution of one of the less “good” resonance forms of an unsaturated

system causes some loss of π-bond strength which is seen as a drop in
observed frequency.
O
O

1684 cm-1 1715 cm-1

C=O C=O

199
 O
C X X= NH2 CH3 Cl NO2
H3C
1677 1687 1692 1700 cm-1

O O
O
N C
H2N C CH3 vs.
O CH3

Strong resonance contributor Poor resonance contributor

(cannot resonate with C=O)

Sterics
 In this case the presence of the methyl group “misaligns” the conjugated
system, and resonance cannot occur as efficiently.

O O

CH3
C=O: 1686 cm-1 C=O: 1693 cm-1
200
 Frequency decreases with increasing atomic mass.

 Frequency increases with increasing bond energy.

Instrument
Design

 Stronger bonds will have higher energy oscillations

Triple bonds > double bonds > single bonds in energy

201
 Classification of IR bands
 Infrared spectrum intensity of signals are classified into four groups
 Strong signals (s): when signal intensity is approximately 5% T.
 Medium signals (m): when signal intensity is between 30 and 60% T.
 Weak signals (w): when signal intensity does not exceed 70% T.

202
 IR spectra interpretation
 There are a few general rules for the determination of a molecular structure.
a. Look first at the high-wavenumber end of the spectrum (>1500 cm−1) and
concentrate initially on the major bands.
b. Do not expect to assign every band in the spectrum.
c. Exploit negative evidence as well as positive evidence. Eg. if there is no
band in the 1850–1600 cm−1 region, it is most unlikely that a carbonyl group
is present.
d. Keep ‘cross-checking’ wherever possible. Eg. an aldehyde should absorb
near 1730 cm−1 and in the region 2900–2700 cm−1.
e. Use the lower-wavenumber end of the spectrum for the confirmation or
elaboration of possible structural elements.
203
 The C-H stretching Region
 Due to the small electronegativity difference between C and H,
hydrocarbon bands are of medium intensity at best and give simple
spectra.

204
C-H sp stretch ~ 3300 cm-1 UNSATURATED
C-H sp2 stretch > 3000 cm-1
C-H sp3 stretch < 3000 cm-1
C-H aldehyde two ~ 2850 and 2750 cm-1 SATURATED
peaks (both weak)

205
205
 The C-H stretching

Methylene group
stretching vibrations

Methyl group stretching

vibrations

206
 Alkanes
 There are two types of bonds (C-H and C-C) and the spectra can be
interpreted in terms of four vibrations.
(a) C-H stretching from 3000–2850 cm-1
(b) C-H bendingC–H bend or scissoring from 1470-1450 cm-1
Instrument
(c) C–H rock, methyl from 1370-1350 cm-1
Design
(d) C–H rock, methyl, seen only in long chain alkanes, from 725-720 cm-1

(c) C-C stretching: are weak, & appear in broad region(1200-800 cm-1)
 C-C stretching is of little value for identification.
(d) C-C bending: (below 500 cm-1, do not appear in normal spectra).
207
Hexane

208
 Alkenes
 The spectra of alkenes are usually more complex (more peaks) than the
spectra of alkanes.

 Frequency of stretching vibrations of –C=C–H bond is higher than –C–

C–H bond in alkanes.

 Only alkenes and aromatics show a C-H stretch slightly >3000 cm-1.

 Modes of vibrations are

 C=C stretch from 1680-1640 cm-1
 =C–H stretch from 3100-3000 cm-1
 =C–H bend from 1000-650 cm-1
209
1-Hexene

210
210
Overlay a spectrum of 1-octene with octane

211
 Alkynes
 The –C≡C– stretch appears as a weak band from 2260-2100 cm-1

 A terminal alkyne (but not an internal alkyne) will show a C–H stretch as
a strong, narrow band in the range 3330-3270 cm-1.

 A terminal alkyne will show a C–H bending vibration in the region 700-
610 cm-1.

 –C≡C– stretch from 2260-2100 cm-1

 –C≡C–H: C–H stretch from 3330-3270 cm-1

 –C≡C–H: C–H bend from 700-610 cm-1

212
 In a manner very similar to alkynes, nitriles show a prominent band
around 2250 due to C≡N bond.

 This band has a sharp, pointed shape just like the alkyne C≡C bond, but
because the C≡N bond is more polar, this band is stronger than in
alkynes.

 The cyano group often gives a strong, sharp peak due to its large dipole
moment.

 The C≡C bond gives a sharp peak, but it is often weak due to a lack of a
dipole.

213
1-Hexyne

214
1-Hexyne

215
 Aromatic
 The aromatic sp2 =C-H stretch occurs at frequencies beyond 3000 cm-1.

 Only alkenes and aromatics show a C–H stretch slightly higher than 3000
cm-1. Compounds that do not have a C=C bond show C–H stretches only
below 3000 cm-1

 Summary
 C–H stretching → 3000-3100 cm-1
 C=C (ring) stretching → 1600-1585 cm-1 and 1500-1400 cm-1
 C–H in-plane bending → 1250-1000 cm-1
 Out of plane =C-H (C-H) stretching (intense) → 900-690 cm-1

216
Aromatic

Toluene

217
O-H stretching

218
 Alcohols have characteristic IR absorptions associated with both the O-H
and the C-O stretching vibrations.

 The free ‒OH band appears as a sharp signal of medium to low intensity
near 3620 cm-1.

 The hydrogen bonded ‒OH band appears as a broad peak between

3400 - 3200 cm-1.

 Summary
 O–H stretch, hydrogen bonded→ 3500-3200 cm-1
 C–O stretch 1260-1050 cm-1 (strong)

219
1-Butanol

220
Cyclohexanol

221
O-H bending
 Alcohols (1260-1000 cm–1) Phenols (1800-1260 cm–1)
 primary alcohol: 1050-1085 cm-1
 secondary alcohol: 1085-1125-1
 tertiary alcohol: 1125-1200 cm-1

222
 Ethers
 The main difference between the IR spectra of ethers and alcohols is
that ethers lack O-H signals.

 The C-O stretching allows for the differentiation of ethers from alkanes.

 Aliphatic ethers: strong band due to asymmetrical stretching,

1150-1085 cm–1 (usually 1125 cm–1)
weak band due to symmetrical stretching

 Alkyl aryl ethers: asymmetrical stretch at 1275-1200 cm-1

symmetrical stretch at 1075-1020 cm–1

 Vinyl alkyl ethers: asymmetrical stretch at 1225-1200 cm-1

symmetrical stretch at 1075-1020 cm–1
223
 N-H Stretching Region

 The N–H stretching of amines are in the region 3500-3200 cm-1.

 It is weaker and sharper than those of the alcohol O–H stretches.

 N-H absorption is of weaker intensity

224
 Summary
 N–H stretching → 3500-3200 cm-1
 1° amine: two bands → 3400-3300 and 3330-3250 cm-1
 2° amine: one band → 3350-3310 cm-1
 3° amine: no bands in this region
 N–H bending (primary amines only) → 1650-1580 cm-1
 C–N stretching (aromatic amines) → 1335-1250 cm-1
 C–N stretching (aliphatic amines) → 1250–1020 cm-1
 N–H wagging (primary and secondary amines only) → 910-665 cm-1

225
IR spectrum of aniline

226
IR spectrum of diethylamine

227
IR spectrum of triethylamine

228
 Carbonyl Stretching Region
 The C=O absorption is one of the most characteristic in the entire
spectrum, and it is also most likely to be the most intense spectral.

 This distinctive carbonyl band is particularly useful for diagnostic

purposes because it has a characteristic high intensity and few other
functional groups absorb in this region.

 C=O stretching of ketones, aldehydes, acids, esters, lactones, acid

halides, anhydrides, amides absorb in the region 1800-1600 cm–1.
229
Ketone
 C=O stretching:
 aliphatic ketones → 1715 ± 10 cm-1
 alpha, beta-unsaturated ketones → 1700-1640 cm-1
 aliphatic C-C-C stretch → 1230-1100 cm-1
 The combination of a C=0 stretch and a C-C-C stretch
are strong evidence for the existence of a ketone in a sample.

230
Acetophenone

231
 Aldehyde
 C-H (H–C=O) stretch → 2850-2700 cm-1 (often two bands are observed)
 C=O stretch:
 aliphatic aldehydes → 1740-1720 cm-1
 alpha, beta-unsaturated aldehydes (aromatic) → 1710-1685 cm-1

232
233
 Carboxylic acids
 O-H stretch → often centered around 3000 cm-1
 C=O stretch:
 Saturated acids → 1730-1700 cm-1
 Aromatic carboxylic acids → 1710-1680 cm-1

234
Benzoic acids

235
 Acid anhydrides
 C=O stretch: 2 bands separated by 60 -30 cm-1)
 Saturated anhydrides, 1750 and 1820 cm-1;
 unsaturated anhydrides, 1775 and 1720 cm-1

1750
1820

236
 Esters
 C=O stretch
 aliphatic →1760-1735 cm-1
 α, β-unsaturated, →1730-1715 cm-1
 phenyl or vinyl esters → 1770-1780 cm–1

237
238
 Amides
 C=O stretch between 1680-1630 cm-1
 N-H stretch
 1° amines show two bands (3370-3170 cm-1)
 2° amines have one band (3370-3170 cm-1)
 3° amines have no absorbance in this region
 N-H bend vibrations between 1640-1550 cm-1

239
240
has C=O band (1650-1800 cm-1) does not have
(very strong
IR Spectrum
C=O band
C-H, O-H, and N-H
3700-2500 cm-1
Aldehyde C≡C , C≡N
C=O 2300 - 2000 cm-1 Alkanes
1740-1720 (saturated) sp3 C-H stretch 2850-3000
1710-1685 (unsaturated) sp3 C-H bend 1460 & 1380
C-H Nitriles Alkenes
C≡N ≈2250
28500-2700 sp2 C-H stretch 3000-3100
Instrument
Ketone sp2 C-H bend 650-1000
Alkynes
C=ODesign C≡C
C=C 1600-1660
≈2150
1715 ± 10 (saturated) sp C-H stretch 3300 Aromatics
1700-1640(unsaturated) sp C-H bend 620 sp2 C-H stretch 3050-3150
sp2 C-H bend 690-900
Esters C=C 1600 & 1480
C=O
1760-1735 (saturated) Alcohols
1730-1715 (unsaturated) O-H stretch 3600-3500
Ethers
C-O stretch 1120 (alphatic)
241
1040 & 1250 (aromatic)
 The IR interpretation is the qualitative tool widely useful in
pharmaceutical ,chemical and fertilize industry’s to identify the functional
groups.
 Identification of functional group and structure elucidation.

 Identification of substances: It is used to differentiate two organic

compounds because the probability that any two compounds will produce
identical spectra is almost zero.

 Studying the progress of the reaction: The rate of disappearance of a

characteristic absorption band of the reactant group and/or the rate of
appearance of the characteristic absorption band of the product group
due to formation of product is observed.

 Detection of impurities: IR spectrum of the test sample can be

determined comparing with the standard compound.
242
 Quantitative Analysis
 The quantity of the substance can be determined either in pure form or
as a mixture of two or more compounds.

 For instance, IR spectroscopy can be used for determining drug content

in pharmaceutical formulations.

 In this, characteristic peak corresponding to the drug substance is

chosen and absorbance of peaks for standard and test sample is
compared.

 The transmittance of each solution versus the reference beam is then

determined at an absorption maximum of the analyte.

 Then transmittance will be related with absorbance

243
Figure 3D.11 The baseline method for determining the
absorbance of an absorption maximum. 244
 IR spectrum provides uniqueness to a degree of specificity that is
matched or exceeded by relatively few other analytical methods.

 This specificity has found particular application to analysis of mixtures of

closely related organic compounds.

 Some of the applications are the following

(a) Analysis of a Mixture of Aromatic Hydrocarbons

(b) Determination of Air Contaminants

245
 Advantages of Infrared Spectroscopy
 It is a universal technique. Solids, liquids, gases, semi-solids, powders,
and polymers are all routinely analyzed.

 Infrared spectra are information rich; the peak positions, intensities,

widths, and shapes in a spectrum all provide useful information.

 It is a relatively fast and easy technique.

 It is also a sensitive technique

 No two molecules will give exactly the same IR spectrum (except

enantiomers)

246
 Disadvantages of Infrared Spectroscopy
 It is impossible to determine
 atoms or monatomic ions because they don’t have chemical bonds.

 homonuclear diatomic molecules due to their symmetry.

 It is also difficult to analyze

 very complex mixtures because sample with complex composition
gives complex spectrum

 Aqueous solutions

247
248
 Reflection

Absorption

Scattering Transimission

249
 History of Raman spectroscopy
C.V. Raman and the Raman Effect
 In 1928, the Indian physicist C. V. Raman
discovered that the visible wavelength of a small
fraction of the radiation scattered by certain
molecules differs from that of the incident beam.

 Furthermore, he noted that the change (shifts) in

frequency depend upon the chemical structure of
the molecules responsible for the scattering.
 His group in Calcutta conducted an extensive
series of measurements of light scattered primarily C.V. Raman
by liquids and also by some solids.
250
 The fundamentals of Raman’s experiment can be outlined as follows

Violet Scattering
Liquid

Light
Rayleigh Raman
Violet filter scattered scattered
light light
 According Raman effect visible wavelength
Green filter
of a small fraction of the radiation scattered
by certain molecules differs from that of the Green
incident beam and furthermore that the
shifts in wavelength depend upon the
chemical structure of the molecules
responsible for the scattering.
251
 Principle to Raman spectroscopy
 Raman spectroscopy is vibrational spectroscopic technique, which
provide a unique molecular fingerprint for any molecule.
 It is a type of spectroscopy which deals with the scattering of light by
the molecules.
 When light is scattered by matter, almost all of the light scattered have
the same wavelength with that of the incident light and called elastic
(Rayleigh scattering).
 However, a very small percentage of light will be scattered with different
wavelength from incident light and called inelastic scattering (Raman
scattering).
 This inelastic scattering of light was observed experimentally by Indian
physicist C. V. Raman and his student in 1928 and then called Raman
scattering (Raman effect).
252
 Light scattering
hv0

Rayleigh
hv0
scattering

hvex ± ΔE 1/ 106 – 108

Raman
scattering
Virtual state

hvex- ΔE hvex+ΔE
hvex hvv
Energy

V3
V2
V1
ΔE ΔE
V0
Ground state
Rayleigh Scattering Stokes Raman scattering Anti-Stokes Raman scattering

253
 Light scattering
hv0

Rayleigh
hv0
scattering

hvex ± ΔE 1/ 106 – 108

Raman
scattering
Virtual state

hvex- ΔE hvex+ΔE
hvex hvv
Energy

V3
V2
V1
ΔE ΔE
V0
Ground state
Rayleigh Scattering Stokes Raman scattering Anti-Stokes Raman scattering

254
 Stokes shifted Raman bands involve the transitions from lower to higher
energy vibrational levels.

 Therefore, stokes bands are more intense than anti-Stokes bands and
hence are measured in conventional Raman spectroscopy.

255
 Selection rules
 Raman effect arises from polarization (distortion of the electron cloud) of
the scattering molecules that is caused by the electric vector of EMR.

 In its distorted form, the molecule is temporarily polarized; that is, it

develops momentarily an induced dipole that disappears on relaxation
and reemission.
µ = αE
µ is induced (not permanent) dipole moment, α is polarizability and
E is applied electric field

 Electron distortion becomes easier as a bond lengthens and harder as a

bond shortens, so the polariza.bility changes as the bound atoms vibrate

256
Polarizability

257
 Homonuclear diatomic molecules such as Cl2 do not absorb IR
radiation, because they have no dipole moment.

 However, homonuclear diatomic molecules do change polarizability

when the bond stretches.

 Example
 1. Cl2 stretching vibration is IR-inactive but Raman active.

 2. Symmetric stretching of CO2 is IR-inactive but Raman

active.

1337 cm-1

Raman active
258
 Raman scattering information is presented as an intensity-versus-
wavelength shift in cm-1 and can be conveniently compared to its IR
counterparts.

 A Raman shift corresponding in frequency to that of the vibrational

mode results.

Figure 3D-1 comparison of

Raman and IR spectra for
mesitylene and indene.

259
 Raman instrumentation
 Raman spectrophotometers can be dispersive or non-dispersive.

 Dispersive Raman spectrophotometer use prism or grating.

 Non-dispersive Raman spectrophotometer uses an interferometer such

as Michelson interferometer in Fourier Transform Raman
spectrophotometer.

FIgure 3D-2 Block diagram of a Raman spectrometer.

260
261
262
 The main components of instrumentation for modern Raman
spectroscopy consists of three components:
 laser source
 sample illumination system
 suitable spectrometer
(1) Source
 The sources used in modern Raman spectrometry are nearly always
lasers because their high intensity is necessary to produce Raman
scattering of sufficient intensity to be measured with a reasonable
signal-to-noise ratio.

 Mercury arc lamp was used as light source in Raman

spectrophotometers in early days.

 435.8 nm line of coiled low-pressure mercury arc lamp was used as

light source until 1960’s.
263
 Laser sources became available in late 1960’s and completely replaced
the mercury lamp.
 Lasers provide strong, coherent monochromatic light in a wide range of
wavelengths and have ability to focus large numbers of photons into
small volumes.
 The sources used in modern Raman spectrometry are nearly always
lasers because their high intensity is necessary to produce Raman
scattering of sufficient intensity to be measured with a reasonable signal-
to-noise ratio.
Table 3D-1 Some common Laser Sources for Raman Spectroscopy

264
 Short wavelength sources such as argon ion and krypton ion lasers can
produce significant fluorescence and cause photodecomposition of the
sample.

 However, long wavelength sources such as diode or Nd:YAG lasers can

be operated at much higher power without causing photodecomposition
of sample and eliminates or reduces fluorescence in most cases

265
(2) Sample Illumination System
 Liquid Samples:
 A major advantage of sample handling in Raman spectroscopy
compared with infrared arises because water is a weak Raman
scattered but a strong absorber of infrared radiation. Thus, aqueous
solutions can be studied by Raman spectroscopy but not by infrared.
This advantage is particularly important for biological and inorganic
systems and in studies dealing with water pollution problems.
 Solid Samples:
 Raman spectra of solid samples are often acquired by filling a small
cavity with the sample after it has been ground to a fine powder.
Polymers can usually be examined directly with no sample
pretreatment.
 Gas samples:
 Gas are normally contain in glass tubes, 1-2 cm in diameter and
about 1 mm thick. Gases can also be sealed in small capillary tubes.

266
(3) Raman Spectrometers
 Raman spectrometers were similar in design and used the same type of
components as the classical ultraviolet/visible dispersing instruments.
 Most spectrometers used double-grating systems to minimize the
amount of stray and Rayleigh-scattered radiation reaching the
transducer. Photomultipliers served as transducers.
 Now Raman spectrometers being marketed are either Fourier transform
instruments equipped with cooled germanium transducers or
multichannel instruments based upon charge- coupled devices.
Wavelength-Selection Devices and Transducers
 A high-quality wavelength-selection device is required in Raman
spectroscopy to separate the relatively weak Raman lines from the
intense Rayleigh-scattered radiation.
 Traditional dispersive Raman spectrometers used double- or even triple-
grating monochromators for this purpose.
267
(3) Raman Spectrometers
 Raman spectrometers were similar in design and used the same type of
components as the classical ultraviolet/visible dispersing instruments.
 Most spectrometers used double-grating systems to minimize the
amount of stray and Rayleigh-scattered radiation reaching the
transducer. Photomultipliers served as transducers.
 Now Raman spectrometers being marketed are either Fourier transform
instruments equipped with cooled germanium transducers or
multichannel instruments based upon charge- coupled devices.
Wavelength-Selection Devices and Transducers
 A high-quality wavelength-selection device is required in Raman
spectroscopy to separate the relatively weak Raman lines from the
intense Rayleigh-scattered radiation.
 Traditional dispersive Raman spectrometers used double- or even triple-
grating monochromators for this purpose.
268
 In recent years, holographic interference filters, called notch filters, and
holographic grating have eliminated the need for multiple-grating
monochromators.

 Instruments with monochromators invariably use photomultiplier tubes as

transducers because of the weak signals being measured.

 Many newer Raman instruments have replaced the single-wavelength

output monochromator with a spectrograph and an array detector.

 The photodiode array was the first array detector to be used. It allows the
simultaneous collection of entire Raman spectra.

 More recently, charge-transfer devices, such as charge coupled devices

(CCDs) and charge-injection devices (CIDs), have been used in Raman
spectrometers.

269
Figure 3D-3 fiber-optic Raman spectrometer with spectrograph and CCD detector.
The bandpass filter (Bp) is used to isolate a single laser line. The band-rejection
filter (BR) minimizes the Rayleigh-scattered radiation.
270
Fourier Transform Raman Spectrometers
 The Fourier transform Raman (FT-Raman) instrument uses a Michelson
interferometer, similar to that used in FTIR spectrometers, and a
continuous-wave (CW).

 It uses NIR lasers (1064-nm source) which virtually eliminates

fluorescence and photodecomposition of samples.

 Holographic notch filters are used to minimize or remove intensity of

Rayleigh-scattered lines from Stokes shifted Raman lines.

 Most FT-Raman instruments instead use InGaAs, and other

photoconductive devices as transducers.

 Raman scattering from a Nd-YAG laser can occur at wavelengths as long

as 1700 nm, and hence photomultipliers and many array detectors are
not used.
271
FIGURE 3D-4 optical diagram of an fT-Raman instrument. The laser radiation passes through the
sample and then into the interferometer, consisting of the beamsplitter and the fixed and movable
mirrors. The output of the interferometer is then extensively filtered to remove stray laser radiation
and Rayleigh scattering. After passing through the filters, the radiation is focused onto a cooled Ge
detector. 272
 IR spectroscopy Raman spectroscopy
 Result of absorption of light by  Due to the scattering of light by the
vibrating molecules. vibrating molecules.
 The vibration is IR active if the dipole  The vibration is Raman active if it causes
moment changes during the a change in polarizability
vibration.

 The vibration should have a dipole  The molecule need not possess a
moment change due to that vibration. permanent dipole moment
 Water generally cannot be used due  Water can be used as a solvent.
to its intense absorption.
 Indicates the ionic character in the  Indicates the covalent character in the
molecule. molecule.
273
Other types of Raman spectroscopy
 Advancements in tunable lasers led to several new Raman
spectroscopic methods in the early 1970s.
1. Resonance Raman spectroscopy
 Resonance Raman scattering refers to a phenomenon in which Raman
line intensities are greatly enhanced by excitation with wavelengths that
closely approach that of an electronic absorption band of an analyte.
 The frequency coincidence (or resonance) can lead to greatly enhanced
intensity of the Raman scattering, which facilitates the study of
compounds present at low concentrations.
 Under this circumstance, the magnitudes of Raman peaks associated
with the most symmetric vibrations are enhanced by a factor of 102 to
106.
 As a consequence, resonance Raman spectra have been obtained at
analyte concentrations as low as 10-8 M.
274
True energy state

Virtual state

V3
Vibrational V2
energy states V1
V0
Ground state
Stokes Anti-stokes Resonance Raman Fluorescence
scattering
Raman scattering

Figure 3D-5. Energy Level Diagram of Raman and Fluorescence Signals.

 Resonance Raman relaxation occurs less than 10-14 s and
 Fluorescence relaxation occurs less than 10-6 to 10-10 s
275
(A) (B)

Figure 3D-5. (A) Raman spectra of β-carotene solution excited at 488, 514,
532 and 633 nm, respectively. The orange dash curves are the baselines
for Raman spectra. (B) The absorbance curve of β-carotene solution in a 2
mm thick cuvette. The numbers with letter ‘C’ represent Raman peaks from
β-carotene, and the numbers with ‘A’ are peaks from acetone molecules.
Journal of Photochemistry & Photobiology, B: Biology 179 (2018) 18–22
276
 The most important application of resonance Raman spectroscopy is to
study biological molecules under physiologically significant conditions;
that is , in the presence of water and at low to moderate concentration.
 As an example, the technique has been used to determine the oxidation
state and spin of iron atoms in hemoglobin and cytochrome-c.
 Non-resonance Raman scattering occurs when the radiation interacts with
a molecule resulting in polarization of the molecule’s electrons. The
increase in energy from the radiation excites the electrons to an unstable
virtual state; and the radiation is emitted (scattered) at a slightly different
energy than the incident radiation.
 Resonance Raman scattering occurs is when the incident radiation is at a
frequency near the frequency of an electronic transition of the molecule of
interest which provides enough energy to excite the electrons to a higher
electronic state.
277
2. Surface-Enhanced Raman Spectroscopy
 In surface-enhanced Raman spectroscopy (SERS), Raman spectra are
acquired in the usual way on samples that are adsorbed on the
roughened surface of or colloidal metal nanoparticles (usually silver, gold,
or copper) or on surfaces of pieces of these metals.
 As a rule of thumb, to achieve maximum Raman signal enhancement, the
target analyte needs to either directly adsorbed on or placed very close to
the metal nanostructure surface.
 In SERS, the Raman signal of the probe molecule is amplified through
excitation of Localized surface plasmon resonance (LSPR) of the
substrate which enhances signal of proximate analyte molecules.
 LSPRs are excited when electromagnetic radiation interacts with a
nanoparticle to create coherent oscillations (excitations) of the conduction
electrons.
278
 -
-- - - +
+ ++ + +
++ +++
- - - --
279

Incident Raman scattering

light

Noble metal nanostructures

 In early days, the Raman signal of the adsorbed molecule are often
enhanced by a factor of 105-106 and even 108-1014 for some systems.
 Surface enhancement is thought to arise from two mechanism

 Electromagnetic Enhancement: the adsorbed molecule experience the

enhanced local electric field near noble metal nanostructure surface
induced by excitation of surface plasmon resonance by both incident and
scattered light.
Enhanced factor: 106-108

 Chemical Enhancement: the polarizability of adsorbed molecule

increases due to metal-molecule charge transfer (CT) complex. Thus, the
CT is in resonance with the incident and scattered photon.

Enhanced factor: 102-103

280
A key to Surface-Enhance Raman spectroscopy

Good Raman scatterers e.g dyes

Probe-metal interactions i.e probe

efficient adsorbtion on the SERS substrate

Au,
Metal nanostructures with dimension
Ag of sub-wavelength, typically <100 nm

Support strongest plasmon resonances i.e

provide large EM field enhancement

 The molecule be attached (or at least brought close) to a metallic substrate 281
Application of Raman spectroscopy(RS)
 Raman spectroscopy finds applications, in variety of fields and industrial
disciplines.

 Raman spectroscopy provides a chemical fingerprint for identification of

a molecule, since vibrational information is specific to the chemical
bonds and symmetry of molecules.

 It is used for characterization and analyses of inorganic substances,

which is superior to IR spectroscopy.

 The vibrational energies of metal-ligand bonds are generally in the range

of 100 to 700 cm-1, a region of the infrared that is experimentally difficult
to study

282
Table 3D-1 Selected Group Frequencies for Common Inorganic Compounds

283
Raman spectroscopy for Organic Species
 Raman spectra are similar to infrared spectra in that they have regions
that are useful for functional group detection and fingerprint regions that
permit the identification of specific compounds.

 Raman spectra yield more information about certain types of organic

compounds than do their infrared counterparts.

 For example, the Raman band of C=C stretch is intense than IR bands,
and its position is sensitive to the nature of substituents as well as to
their geometry.

 However, in the IR the intensity is highly variable and may range from
very strong to completely missing.

 Thus, Raman studies are likely to yield useful information about the
olefinic functional group that may not be revealed by IR spectra.
284
Figure 3D-6 Raman and IR spectra for 1-Hexene

285
Figure 3D-7 Raman and IR spectra for cis-3-Heptene

286
Figure 3D-8 Raman and IR spectra for tran-3-Heptene

287
2. Material science
 Raman spectroscopy is suitable technique for
 characterization of nanomaterials as nanocomposites, nano-sized
crystals, polymers and semiconductors.
 real-time monitoring of polymerization reactions.
 determination of semiconductor impurities in silicone substrates and
diamond-like carbon coatings.
α-Fe2O3 nanoflakes

Carbon-coated/Fe3O4 nanoflakes

Figure 3D-9 Raman spectra of different nanomaterials such as metal-oxide

nanostructures and nanocomposites. 288
3. Forensic sciences.
 RS used in forensic science for rapid identification of trace amounts of
substances in evidential materials such as paints, inks from documents,
explosive, illegal drugs, gunpowder residues, chemical and biological
agents, plastics etc.

Figure 3D-10. Raman spectra of cocaine samples in different forms: (A) yellow freebase paste, (B)
white freebase paste, (C) crack rock, (D) hydrochloride cocaine powder, and (E) freebase cocaine
powder. J. Raman Spectrosc. 2016, 47, 28–38 289
 RS also used in security forces and fire brigades for identification of
unknown or hazardous substances, by instance detection of explosives.

Figure 3D-11 Raman spectra of trinitrotoluene (TNT) on blue denim and

leather, together with the spectra of the uncontaminated fabrics.
290
4. Biological Applications
 Raman spectroscopy has been applied widely for the study of biological
systems.
 Raman spectroscopy involve e. g. DNA analyses, prognoses and
diagnoses of carcinomas, study of biological systems, etc.

Figure 3D-12: Standard Raman (A) and SERS (B) spectra of two different (i, ii) double-
stranded thiolated DNA oligomers J. Am. Chem. Soc. 2008, 130, 5523–5529 291
Figure 3D-13 SERS spectra of three bacterial meningitis pathogens (a) SERS spectra of
N. meningitides, (b) H. influenzae and (c) S. pneumoniae using PCR product of different
concentrations.
292
Advantages of Raman spectroscopy
 Quantitative analysis using Raman spectroscopy is more simpler than IR
spectroscopy of due to the following reason.
 Raman spectra tend to be less cluttered with bands than IR spectra
and there is less peak overlap in mixtures
 suitable for analysis many organic and inorganic materials (solids,
liquids, polymers or vapors).
 Less or no- sample preparation needed.
 not interference from water.
 non-destructive.
 highly specific
 Raman spectra are acquired quickly within seconds.
 samples can be analyzed using glass or a polymer cell.
 A very small volume a (< 1 μm in diameter) is required
 inorganic materials are easily analyzable with Raman spectroscopy.
293
Disadvantages of Raman spectroscopy
 Very low Raman scattering effect
 high levels of fluorescence (intrinsic or caused by impurities) overlaying
the Raman bands.
 intense laser radiation leads to sample photodecomposition
 Expensive instrument and maintenance fee

294
295
 Introduction of NMR spectroscopy
 Nuclear magnetic resonance, NMR, is a physical phenomenon of
resonance transition between magnetic energy levels, happening when
atomic nuclei are exposed to external magnetic field and applied an EMR
with specific frequency (radio- frequency region of roughly 4 to 900 MHz).

 Unlike other spectroscopic methods, nuclei of atoms rather than outer

electrons are involved in the absorption process.

 NMR spectroscopy operates by applying a magnetic field to cause nuclei

to develop the energy states and then measuring the amount of energy
necessary to put various nuclei in resonance.

 An NMR spectrum provides a signal or peak representing the energy

necessary to bring each nuclei into resonance.
296
 Magnetic Resonance
Nuclear spins
 Nuclei have a positive charge and when certain nuclei rotate about an
axis it will have the property of spin.

 The spinning charged nucleus generates a magnetic field and the

nucleus behave like a tiny magnet.

 Therefore, a spinning nucleus acts like magnet oriented along the spin
rotation axis. This tiny magnet is often called a nuclear spin.
297
 Nuclear Resonance
 When a spinning nucleus is placed in a strong external magnetic field, B0,
the spinning nucleus will have a small magnetic moment, µ.

 The magnetic fields of the spinning nuclei will tends to align itself either in
the same direction (+½ or α) of the external magnetic field (B0) or
opposite direction (-½ or β) to it.

298
 NMR spectroscopy employs an magnetic energy absorption process,
which orients spinning nuclei in a strong external magnetic field.
alignment opposes
the applied magnetic
field and is higher in
energy.

∆ = hv

alignment with the

Magnet applied magnetic field
and is lower in
energy.
Influence of applied magnetic field

Figure 3E-1: Nuclear Spin Energy Levels

299
 If we irradiate the precessing nuclei with a beam of radio frequency, the
low energy nuclei may absorb this energy and move to a higher energy
state.

 The precessing nuclei will absorb energy from the radio frequency
source, and if the precessing frequency is the same as the frequency of
the radio frequency beam.

 When this occurs, the nucleus and radio frequency beam are said to be
resonance, hence the term “ nuclear magnetic resonance”:

 In NMR spectroscopy, resonance is the absorption of energy by a

precessing nucleus and the resulting “flip” of its nuclear spin from a lower
energy state to a higher energy state.

300
 NMR spectrometer

Figure 1E-4 700 MHz NMR Spectrometer.

301
 NMR spectrometer

Figure 1E-5 Block diagram of an FT-NMR spectrometer.

302
 Essentials of an NMR spectrometer are a powerful magnet, a radio-
frequency generator, and a radio-frequency reciever.

 The sample is dissolved in a solvent, most commonly

 CCl4 - carbon tetrachloride
 CS2 - carbon disulfide
 CDCl3 - Deuteriochloroform
 C6D6 - Hexa deuteriobenzene
 D2O – Deuterium oxide,
 and placed in a sample tube which is then suspended in the magnetic
field and set spinning.

 Using a Fourier transform NMR (FT-NMR) spectrometer, a spectrum can

be recorded in about 2 seconds.
303
 NMR spectrometer.
 There are two general types of NMR spectrometers:
 Wide-line instruments have magnets with strengths of a few tenths of a
tesla and are considerably simpler and less expensive than are high-
resolution instruments.
 High-resolution instruments are equipped with magnets with strengths
that range from 1.4 to 23.5 T, which correspond to proton frequencies of
60 to 1000 MHz (1 GHz).

Figure 3E-6 NMR spectra of ethanol at a frequency of 60 MHz. Resolution:

(a) ~1/106; (b) ~1/107. 304
 Environmental effects of NMR spectra
 The frequency of RF radiation that is absorbed by a given nucleus is
strongly affected by its chemical environment-that is, by nearby electrons
and nuclei.
Types of Environmental Effects
 The chemical environment of the nuclei influences the instrumental
response.

 The information from the spectra can be broken into

a) Number of Signals
b) Position of Signals (Chemical Shift)
c) Splitting of Signal (Spin-spin splitting)

305
(a) Number of Signals
 Shows number of different chemical environments in which the nuclei in
the sample reside.

 It shows how many different kinds of protons are present

 The protons that reside in the same magnetic environment are termed
chemically equivalent protons.

306
(b) Splitting of Signals (Spin-Spin Splitting)
 The splitting of chemical-shift resonances occurs as the magnetic
moment of a nucleus interacts with the magnetic moments of immediately
adjacent nuclei.

 Example: it shows the number of protons on adjacent atoms.

 The pattern into which some signals split indicates the number of protons
on adjacent atoms.

 There will be n + 1 peaks for n protons on adjacent atoms.

 The number of such peaks is referred to as the multiplicity

307
 Table 3E-1: Relative Intensities of First-order Multiplets (I = 1/2)

 The spacing between the peaks in hertz is called the coupling constant,
J.

 Two signals that arise from nuclei that interact with each other will have
the same value of J.
308
309
(c) Position of Signals (Chemical Shift)
 The chemical shift is telling us the strength of the magnetic field that the
nucleus feels.

 The shift in the position of the NMR region resulting from the shielding
and deshielding by electrons is called chemical shift.

 The chemical shift for nuclei is represented as follows.

Chemical shift =

 where is the resonant frequency of a specific nucleus;

, the resonant frequency of the reference nucleus; and
, the spectrometer frequency.
310
 In order to make these numbers easier to handle, it is multiplied by 106
and then expressed in ppm.

 The symbol for the chemical shift is δ. It is expressed a

δ= × 10 ppm

 The chemical shifts of nuclei are measured (and defined) relative to a

standard nucleus.

 A popular standard for proton NMR is tetramethylsilane (TMS), which has

the chemical formula Si(CH3)4.

 In TMS all 12 hydrogen nuclei are chemically equivalent; that is, they are
all exposed to the same shielding and give a single absorption peak.
311
 Nucleus feel different magnetic fields depending upon their location and
the neighbour atom they directly attached to.

 Since the field experienced by the nucleus defines the energy difference
between the two spin states, the frequency and hence, the chemical shift,
δ /ppm, will change depending on the electron density around the proton.

 When a proton is present inside the magnetic field more close to an

electro positive atom more applied magnetic field is required to cause
excitation. This effect is called shielding effect.

 When a proton is present outside the magnetic field close to a

electronegative atom less applied magnetic field is required to cause
excitation . This effect is called deshielding effect

312
Shielding
 Under an applied magnetic field, circulating electrons in the electron
cloud produce a small opposing magnetic field, ultimately decreasing the
effective magnetic field, shifting the signal to the right (or up field).
 If there is higher electron density around the nucleus, the electron cloud
“shields” the nucleus from the applied magnetic field, resulting
diamagnetic shielding.
 Because the nucleus experiences lower external magnetic field, it needs
a lower frequency to achieve resonance, and it shifts chemical
shift upfield (lower ppm).

B0 B0
e- e- e-
Magnet

Magnet
e- - e- e-
- e
e e-
313
Deshielding
 If the electron density around a nucleus decreases, the opposing
magnetic field becomes small and therefore, the nucleus feels more the
external magnetic field B0, and therefore it is said to be deshielded.

 Because the proton experiences higher external magnetic field, it needs a

higher frequency to achieve resonance, and therefore, the chemical shift
shifts downfield (higher ppm)

B0
Magnet

Magnet

314
 Magnet Magnet
RF
RF
e- e-
e-

shielded Deshielded
Low E High E
resonance

315
Figure 3E-7 Abscissa scales for NMR spectra. 316
 Effective Magnetic Field, Beff is what the nuclei sense through its
electron filled environment.
Beff= Bapplied – Blocal → for shielding
 Bapplied is the magnetic field supplied by the applied external magnetic
force (NMR spectrometer). This number is the same for all the nuclei in
the molecule.

 Blocal is the magnetic field supplied by the surrounding electrons around

the nuclei. This number varies between nuclei in the molecule.

 According to this formula, the greater the electron density is around the
nuclei, the larger the Blocal will be, and the more the proton is shielded
from the applied magnetic field.

317
 Factors affecting Chemical shift

1. Electronegativity (inductive effect)

2. Magnetic anisotropy

3. Hydrogen bonding

318
1. Electronegativity
 Electronegative atoms pull electron density from the proton toward itself .

 This causes the proton to have less electron density, and the proton is
said to be less shielded (deshielding).
d- d+
Cl C H
d-
 The less shielded proton feels more applied magnetic field, and this leads
to a higher E and a higher chemical shift.

 Protons that are closer to the electronegative atom are in a less electron
dense environment, which means that their chemical shifts will be larger.

319
 Electronegativity dependence of Chemical Shift
Dependence of the Chemical Shift of CH3X on the Element X

Compound CH3X CH3F CH3OH CH3Cl CH3Br CH3I CH4 CH3)4Si

Compound CH3X F O Cl Br I H Si

Electronegativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8

Chemical shift d 4.28 3.40 3.05 2.68 2.16 0.23 0

Most deshielded TMS

deshielding increases with the electronegativity of atom X

320
 Substitution Effects on Chemical Shift

most CHCl3 CH2Cl2 CH3Cl

deshielded 7.27 5.30 3.05 ppm

The effect increases with greater numbers of electronegative atoms.

most -CH2-Br -CH2-CH2Br -CH2-CH2CH2Br

deshielded 3.30 1.69 1.25 ppm

The effect decreases with increasing distance.

321
 2. Magnetic Anisotropy Effect
 The presence of a nearby π-bond or π-system greatly affects the
chemical shift.

 Magnetic anisotropy means that there is a "non-uniform magnetic field“

due to non-uniform electron density in all directions.

 In compound containing double or triple bond circulation of π-electrons

about nearby nuclei interact with applied magnetic field to generate an
induced magnetic field

 This can either oppose or reinforce the location of proton or the space
occupied by the proton causing either shielding or deshielding effect.

322
Aromatic Protons d = 7-8 ppm Vinyl Protons d = 5-6 ppm

Acetylene Protons , d = 2.5 ppm Aldehyde Proton d = 9-10 ppm

Electronegative
oxygen atom

323
3. Hydrogen bonding
 The chemical shift depends on how much hydrogen bonding is taking
place.
 Hydrogen bonding lengthens the O-H bond and reduces
the valence electron density around the proton -it is
R deshielded and shifted downfield in the NMR spectrum.

O H H

O H O R
R
 Alcohols vary in chemical shift from 0.5 ppm (free OH) to
about 5.0 ppm (lots of H bonding).

 Hydrogen bonding in concentrated solutions deshield the protons, so

signal is around = 3.5 for N-H and  = 4.5 for O-H.
324
 Carboxylic acids have strong hydrogen bonding – they form dimers.
O H O
R C C R
O H O

 With carboxylic acids the O-H absorptions are found between 10 and 12
ppm very far downfield.

H3C O  In methyl salicylate, which has strong

O
H internal hydrogen bonding, the NMR
absorption for O-H is at about 14 ppm, way,
O
way downfield.

325
Proton NMR Shifts

326
Interpretation of 1H NMR spectra

327
 Proton NMR spectrum
 How many types of H ?
 The number of signals shows how many different kinds of protons are
present?
 Where on spectrum?
 The location of the signals shows how shielded or deshielded the
proton is-Chemical shift
 How big?
 Indicated by the integration (relative area) of the signal for each
group. The intensity of the signal shows the number of protons of that
type.
 What is the connectivity ?
 Look at the coupling patterns. This tells you what is next to each
group
328
Spin-spin splitting
 Signal splitting: Splitting of an NMR signal into a set of peaks by the
influence of neighboring nonequivalent hydrogens.

 Peak: The units into which an NMR signal is split is doublet, triplet,
quartet, multiplet, etc.

 (n + 1) rule: If a hydrogen has n hydrogens nonequivalent to it but

equivalent among themselves on the same or adjacent atom(s), its 1H-
NMR signal is split into (n + 1) peaks.

329
Example-1: For each of the following compounds, calculate the number of
multiplets for each band and their relative areas:
(a) Cl(CH2)3Cl; (b) CH3CHBrCH3; (c) CH3CH2OCH3.

(a) ClCH2CH2CH2Cl (b) CH3CHBrCH3

6 +1 = 7
4 +1 = 5

2 +1 = 3 1 +1 = 2
(a) CH3CH2OCH3
0 +1 = 1
3 +1 = 4
2 +1 = 3
330
=>

331
13C NMR Spectroscopy

332
 Sensitivity of Carbon NMR
 About 99% of the carbon atoms in a natural sample are the isotope 12C.

 12Cisotope has an even number of protons and neutrons, so it has no

magnetic spin and cannot give rise to NMR signals. .

 The less abundant isotope 13C has an odd number of neutrons, giving it
a magnetic spin ½ of just like a proton.

 The sensitivity of 13C decreased by a factor of 100 because of the

presence of only 1% 13C magnetic isotope.

333
 Still 13C NMR has several advantages over proton NMR in terms of its
power to elucidate organic and biochemical structures.

 First, 13C NMR provides information about the backbone of molecules

rather than about the periphery.
 In addition, there is less spectral overlap in 13C spectra than in proton
spectra because δ range for 13C for most organic compounds is about
200 ppm, compared with 10 to 15 ppm for the proton.

334
Carbon Chemical Shifts
 Like 1H NMR, many 13C signals are deshielded by electron-withdrawing
substituents → has a substantial effect for a carbon atom.
 Carbon chemical shifts are ~15 to 20 times larger than proton
chemical shifts, because the carbon atom is one atom closer to a
shielding or deshielding group than its attached hydrogen.
 For example, consider 1H NMR and 13C NMR spectra of 1,2,2-
trichloropropane.

335
 Similarly, an aldehyde proton absorbs at around δ = 9.4 1H NMR in the
spectrum, and the carbonyl carbon atom absorbs around 180 ppm
downfield.

Figure 3E-8: 1H NMR (lower) and 13C NMR (upper) spectra of a

heterocyclic aldehyde 336
Spin-Spin Splitting
 13C NMR, splitting patterns are quite different from those observed in 1H
NMR.

 Since only 1% of the carbon atoms in the 13H NMR sample are
magnetic, there is only a small probability of natural two 13C atoms
occurring adjacent to each other is small.

 Furthermore, coupling between 13C and 12C does not occur because the
spin quantum number of 12C is zero.
 Therefore, carbon–carbon splitting can be ignored. However, carbon–
hydrogen coupling is common.
 Most carbon atoms are bonded directly to hydrogen atoms or are
sufficiently close to hydrogen atoms for carbon–hydrogen spin-spin
coupling to be observed. 337
 The two most common types of proton decoupling in 13C NMR are
 broadband decoupling;
 off-resonance decoupling; and

(a) Broadband Decoupling

 Here simple 13C NMR spectra are recorded by continuously irradiating
the proton with a broadband (“noise”) proton transmitter.

 As a result, all the protons are continuously in resonance, and they

rapidly flip their spins.

 The carbon nuclei see an average of the possible combinations of

proton spin states.

 Each carbon signal appears as a single, unsplit peak because any

carbon–hydrogen splitting has been eliminated. 338
(b) Off-Resonance Decoupling
 Proton spin decoupling produces spectra that are very simple, but some
valuable information is lost in the process.

 For off-resonance decoupling, the 13C nuclei are split only by the protons
directly bonded to them and n + 1 rule applies.

 Off-resonance-decoupled spectra are easily recognized by the

appearance of TMS as a quartet at 0 ppm, split by the three protons of
each methyl group.

 For example, consider off-resonance-decoupled 13C NMR spectrum of

1,2,2-trichloropropane.

339
 The CCl2 group appears as a singlet,
the CH2Cl group as a triplet, and the
CH3 group as a quartet.

Figure 3E-9: Off-resonance-decoupled 13C NMR spectrum of 1,2,2-

trichloropropane
340
Figure 3E-10: Off-resonance-decoupled (upper) and broadband-
decoupled (lower) 13C NMR spectra of butan-2-one.

341
Depth 13C NMR
 DEPT (Distortionless Enhanced Polarization Transfer) is a more recent
technique.
 DEPT gives better sensitivity, and it avoids overlapping multiplets
because all the peaks remain decoupled singlets.
 Each 13C nucleus is magnetically coupled to the protons bonded to it.
 A DEPT experiment usually includes three spectral scans:
 The normal decoupled scan, in which each type of nucleus appears as a
singlet.
 The DEPT-90 scan, in which only the CH (methine) carbons bonded to
exactly one proton appear.
 The DEPT-135 scan, in which the (methyl) groups and CH (methine)
groups appear normally, and the CH2 groups give negative peaks.
However, carbons that are bonded to no protons do not appear.
342
 In general
 Carbons with no H’s appear only in the
normal spectrum, but not in either
DEPT spectrum.

 Methine carbons (CH) give normal

positive peaks in all three spectra.

 Methylene carbons give normal peaks in

the normal spectrum, no peaks
in the DEPT-90 spectrum, and negative
peaks in the DEPT-135 spectrum.

 Methyl carbons give normal peaks in the

normal spectrum, no peaks in the DEPT-
90 spectrum, and normal peaks in the
DEPT-135 spectrum
Figure 3E-12 13C NMR spectrum and DEPT spectra of
but-3-en-2-one

343
Table 13-4 Summary of DEPT Spectra

344
Interpreting Carbon NMR Spectra

345
 Interpreting 13C NMR spectra uses the same principles as interpreting
1H NMR spectra.

 The spectrum provides the following information:

 The number of different signals implies how many different types of
carbons are present.

 The chemical shifts of those signals suggest what types of functional

groups contain those carbon atoms.

 The splitting of signals in the off-resonance-decoupled spectrum or

the DEPT-90 and DEPT-135 spectra indicate how many protons are
bonded to each carbon atom.

346
Figure 3E-14 Off-resonance-decoupled and broadband-decoupled
spectra of δ-valerolactone of molecular formula C5H8O2. 347
 The chemical shift of 70 ppm is about 20 times the chemical shift
of a proton on a carbon bonded to an electronegative element.

 The signal at 30 ppm corresponds to a carbon atom bonded to a

carbonyl group. Remember that a proton on a carbon adjacent to
a carbonyl group absorbs around 2.1 ppm, and we expect the
carbon to have a chemical shift about 15 to 20 times as large.

 The two signals at 19 and 22 ppm are from carbon atoms that are
not directly bonded to any deshielding group, although the carbon
at 22 ppm is probably closer to one of the oxygen atoms.

348
349
 Introduction
 Mass spectrometry is a technique used for measuring the molecular
weight and determining the molecular formula of an organic compound.

 A molecules ionizes in a high vacuum by bombardment with a beam of

high-energy electrons & knock out an additional electron.

M + e- → [M] +• + 2e-

 The radical cation M+• is called the molecular ion or parent ion and the
mass of M+• represents the molecular weight of M.

 The ions are sorted according to their mass to charge ratios (m/z), and
and relative abundances
350
 Since M is unstable, some ions decompose to form fragments of radicals
and cations that have a lower molecular weight than M+•.

 The ions of smaller molecular weights are called fragments.

 Bombardment of molecules by energetic electrons, produces the

molecular ion and several fragments both charged and uncharged.

 But only the positively charged fragments are detected by the mass
spectrometer.
351
 Molecular ion (M): A radical cation formed by removal of a single electron
from a parent molecule in a mass spectrometer.

 For our purposes, it does not matter which electron is lost; radical cation
character is delocalized throughout the molecule.

 Therefore, we write the molecular formula of the parent molecule in

brackets with
 a plus sign to show that it is a cation.
 a dot to show that it has an odd number of electrons.

352
 Mass Spectrometer

Figure 3F-1 Schematic of a mass spectrometer

353
 Mass spectrometers
 Instrument that produces ions and separate them according to their mass
to charge ratios, m/z.

 Following are components of mass spectrometer

1) Sample inlet system

2) Ion sources

3) Mass analyzer

4) detectors

5) Readout

354
 The MS instrument consists of three major components:
 Ion Source: For producing gaseous ions from the substance being
studied.

 Mass Analyzer: For resolving the ions into their characteristics mass
components according to their mass-to-charge ratio.

 Detector System: For detecting the ions and recording the relative
abundance of each of the resolved ionic species.

355
 A mass spectrometer should always perform the following processes:
 Produce ions from the sample in the ionization source.

 Separate these ions according to their mass-to-charge ratio in the

mass analyzer.

 Eventually, fragment the selected ions and analyze the fragments in

a second analyzer.

 Detect the ions emerging from the last analyzer and measure their
abundance with the detector that converts the ions into electrical
signals.

356
 Separation of Ions:
 A beam of electrons causes molecules to ionize and fragment.

 The mixture of ions is accelerated and passes through a magnetic field,

where the paths of lighter ions are bent more than those of heavier
atoms.

 By varying the magnetic field, the spectrometer plots the abundance of

ions of each mass.

 The exact radius of curvature of an ion's path depends on its mass-to-

charge ratio, symbolized by m/z. In this expression, m is the mass of the
ion (in amu) and z is its charge.

 The vast majority of ions have a +1 charge, so we consider their path to

be curved by an amount that depends only on their mass.. 357
Molecular Mass Spectra
 A mass spectrum is a plot of the amount of each cation (relative
abundance) versus its mass to charge ratio (m/z, where m is mass, and z
is charge).

 Since z is almost always +1, m/z actually measures the mass (m) of the
individual ions.

Figure 3F-2 Mass spectrum of ethyl benzene 358

 The collision between energetic electrons and analyte molecules usually
imparts enough energy to the molecules to leave them in an excited
state.

 Relaxation then often occurs by fragmentation of part of the molecular

ions to produce ions of lower masses.

 The tallest peak in the mass spectrum is called the base peak.

 The base peak may also be the M peak, but not always.

359
 Isotopes
 The presence of significant amounts of heavier isotopes leads to small
peaks that have masses that are higher than the parent ion peak.

Table 3E-1 Natural abundance of Isotopes of Some Common elements

360
M+1 Peaks
 Though most C atoms have atomic mass of 12, ≈1% have a mass of 13.

 Thus, 13C is responsible for the peak called the M + 1 peak.

Figure 3F-3 Mass spectrum of hexane (CH3CH2CH2CH2CH2CH3), C6H14

361
M+2 Peaks
 The most common elements giving rise to significant M + 2 peaks are
chlorine and bromine.
 Chlorine in nature is 75.77% 35Cl and 24.23% 37Cl.
 A ratio of M to M + 2 of approximately 3:1 indicates the presence of
a single chlorine atom in a compound

Also note the drop of 35/37

(64-29 = 35; 66-29 = 37)
Halogens can fragment readily

Figure 3E.4 Mass spectrum of MS of chloroethane 362

M+2 Peaks
 Bromine in nature is 50.7% 79Br and 49.3% 81Br.
 A ratio of M to M + 2 of approximately 1:1 indicates the presence of a
single bromine atom in a compound

Figure 3E-5 Mass spectrum of MS of 1-bromopropane

 Sulfur is the only other element common to organic compounds that
gives a significant M + 2 peak
32S = 95.02% and 34S = 4.21%
363
 Sulfur is the only other element common to organic compounds that
gives a significant M + 2 peak
 M+2 larger than usual (4% of M+)
32S = 95.02% and 34S = 4.21%

Figure 3E-6 Mass spectrum of MS of diethyl sulfide

364
 Molecular Ions and Interpreting a mass spectrum
 The only elements to give significant M + 2 peaks are Cl and Br

 If no large M + 2 peak is present, these elements are absent.

 Is the mass of the molecular ion odd or even?

 Nitrogen Rule: If a compound has

 the m/z value of the molecular ion is always an even number if the
molecular ion contains either zero or an even number of nitrogen
atoms.
 Whereas, molecular ion will have an odd m/z value if there are odd
number of nitrogen atoms,.

365
Examples: C6H5CH2NH2 MW =107
H2NCH2CH2NH2 MW = 60

Table 3E-2 Molecular weight of Nitrogen containing compound

366
 Fragmentation patterns of alkanes
 The mass spectra of simple hydrocarbons have peaks at m/z values
corresponding to the ions produced by breaking C-C bonds.

 Peaks can occur at

 the stability of the carbocation formed affects its abundance

 the more stable the cation the higher the peak
 the more alkyl groups attached to the carbocation the more stable it is
tertiary 3° > secondary 2° > primary 1°

 alkyl groups are electron releasing and stabilise the cation

367
1. Octane

Sequential peaks 14 mass units apart

368
2. Isooctane

 Branched alkane forms most

stable carbocation

369
 Fragmentation patterns of alkenes
 The molecular ion of alkenes, is usually distinct especially in compounds
containing multiple double bonds.

 Shows fragment ions of CnH2n+ and CnH2n-1+ than the CnH2n+1 peak of
alkanes.

 The most common fragmentation of alkenes is cleavage of an allylic bond

to give a resonance-stabilized allylic cation.

370
Figure 3E-7 The radical cation of trans-hex-2-ene cleaves at an
allylic bond to give a resonance-stabilized methallyl cation, m/z = 55.
371
 Fragmentation patterns of aromatic
 Compounds containing aromatic rings tend to fragment at the carbon
(called a benzylic carbon) next to the aromatic ring. Such a cleavage
forms a resonance-stabilized benzylic cation.

372
 Fragmentation patterns of alcohol
 One of the most common fragmentation patterns of alcohols is loss of
H2O to give a peak which corresponds to M-18.

 Another common pattern is loss of an alkyl group from the carbon

bearing the OH to give a resonance-stabilized oxonium ion and an alkyl
radical. This fragmentation is called an alpha cleavage

373
Figure 3E-8: The mass spectrum of 3-methylbutan-1-ol. The strong peak at m/z 70 is actually the
M–18 peak, corresponding to loss of water. The molecular ion is not visible because it loses water
easily. 374
 Evaluation of Unknown Compounds by Mass Spectroscopy
1. Get an overview of the spectrum. Is it simple? Complex? Are there
groups of peaks?

2. Identify and evaluate the molecular ion.

 Is M+ strong or weak?

 Are there significant peaks due to isotopes (e.g. M+1, M+2, etc.)?

 Is the molecular ion an odd number (Apply the Nitrogen Rule)?

 If a molecular formula is not provided, check tables or on-line

calculators to determine possible formulas

375
3. Evaluate the major fragments
 What mass is lost from M+ to give these peaks?

 What ions could give these peaks?

 If available, use IR data to identify functionality, and consider known

fragmentation patterns of these groups.

 Consider the loss of small neutral molecules (e.g. H2O, H2C=CH2,

HC≡CH, etc.)

4. Use fragmentation information to piece together possible structure

376
377
 Introduction to Atomic Spectrometry
 Atomic spectrometry is the most widely used method for elemental
analysis.

 In all atomic spectroscopic techniques, we must atomize the sample,

converting it into gas-phase atoms and ions.

 Gaseous atoms then absorb ultraviolet-visible radiations followed by

measurement of ultraviolet-visible light absorption, emission and
fluorescence by atomic species in the vapor.

 Absorbance or emission can be measured and is related to

concentration of analyte.
378
 Origins of Atomic spectra
 In atomic spectrometry the valence electrons are responsible for atomic
spectra observed in a process of absorption or emission of radiation.

 At room temperature, essentially all atoms are in the ground state.

 As an electron is excited to a higher energy level, it will absorb energy

exactly equal to the energy difference between the two states.

 Atoms or ions in gas-phase → no vibrational or rotational energy states.

 This absence means that only electronic transitions occur.

 Thus, atomic emission, absorption, and fluorescence spectra are made up

of a limited number of narrow spectral lines.
379
 Electron excitation
 The excitation can occur at different degrees
 First low E tends to excite the outmost electrons
 when excited with a high E (photon of high v) an electrons can jump
more than one levels
 even higher E can tear inner electrons away from nuclei.

380
 Excitation of electrons in ground state atoms requires an input of
sufficient energy to transfer the electron to one of the excited state.

 Excited electrons will only spend a short time in the excited state where
upon relaxation an excited electron will emit a photon and return to the
ground state.

Figure 4A-1 Emission, absorption, and fluorescence by atoms in a flame.

381
 Emission Spectra
 In atomic emission spectroscopy, analyte atoms are excited by heat or
electrical energy

 The energy typically is supplied by

 a plasma,
 a flame,
 a low-pressure discharge, or
 by a high-powered laser.

 A transition to or from the ground state is

called a resonance transition, and the
resulting spectral line is called a
resonance line.
Figure 4A-1 Origin of three sodium emission lines
382
 Absorption Spectra
 In atomic absorption spectroscopy, an external source of radiation
impinges on the analyte vapor.
 If the source radiation is of the appropriate
frequency (wavelength), it can be absorbed
by the analyte atoms and promote them to
excited states. (b)
(a)

Figure 4A-2 (a) Partial absorption spectrum for sodium vapor. (b)
Electronic transitions responsible for the absorption lines in (a) 383
 The techniques of atomic spectroscopy can be divided into three
categories.
 Atomic absorption spectrometry
 Atomic emission spectrometry
 Atomic fluorescence spectrometry

384
 Atomization methods
 The atomization device must normally perform the complex task of
converting analyte species in solution into gas-phase free atoms and/or
elementary ions
 To obtain atomic spectra, the constituents of a sample must be converted
to gaseous atoms.

 In atomic spectroscopy, analyte can be atomized in a flame, an

electrically heated furnace, or a plasma.

Flame Furnace
plasma 385
 Atomization – the process by which a sample is converted to an atomic
vapor.

 Atomizer – a device used to converted a sample to an atomic vapor.

Table 4A-1 Types of atomizers used for atomic Spectroscopy

Typical Atomization
Type of Atomizer
Temperature, °C
Flame 1700–3150
Electrothermal vaporization (ETV) 1200–3000
Inductively coupled argon plasma (ICP) 1200–3000
Direct current argon plasma (DCP) 4000–6000
Microwave-induced argon plasma (MIP) 2000–3000
Laser-induced plasma 8000–15,000
Glow-discharge (GD) plasma Nonthermal
Electric arc 4000–5000
386
B. Atomizers
 Atomization is separation of particles into individual molecules and
breaking molecules into atoms

 Flame atomization

387
Several processes occur during atomization including:
a) nebulization – solution sample, get into fine droplets by spraying via thin
nozzle or passing over vibrating crystal.

b) desolvation - heat droplets to evaporate off solvent just leaving analyte

and other matrix compounds

c) volatilization – convert solid analyte/matrix particles into gas phase

d) dissociation – break-up molecules in gas phase into atoms.

e) ionization – cause the atoms to become charged

f) excitation – with light, heat, etc. for spectra measurement.

388
Sample aerosol

389
 Introduction of solution samples
 There are several sample introduction system in atomic spectroscopy.

Table 4A-2 Methods of Sample introduction in atomic spectroscopy

390
Pneumatic Nebulizers
 Samples in solution are usually easily introduced into the atomizer by a
simple nebulization, aspiration, process.
 Nebulization converts the solution into an aerosol of very fine droplets
using a jet of compressed gas.

 The flow of gas carries the aerosol droplets to the atomization chamber
or region.

Figure 4A-4 Types of pneumatic nebulizers: (a) concentric tube, (b) cross-flow, (c) fritted disk, (d)
Babington. 391
 Introduction of Solid Samples
 Several techniques have been used for the direct introduction of solids into
atomizers.
(a) Direct sample Insertion
 direct manual insertion of the solid into the atomization device
(b) Electrothermal vaporization
 vaporization of the sample and transfer of the vapor into the atomization
region,
(c) Arc or spark ablation
 arc, spark, or laser ablation of the solid to produce a vapor that is then
swept into the atomizer,
(d) Glow-Discharge Technique
 slurry nebulization in which the finely divided solid sample is carried
into the atomizer as an aerosol consisting of a suspension of the solid
in a liquid medium, and sputtering in a glow-discharge device 392
 Atomization techniques
1. Flame atomization
 In a flame atomizer, a solution of the sample is nebulized by a flow
of gaseous oxidant, mixed with a gaseous fuel, and carried into a
flame where atomization occurs.

 Most flame spectrometers use a premix burner, in which fuel,

oxidant, and sample are mixed before introduction into the flame.

 Flames are regarded as continuous atomizers since samples are

continuously introduced and a constant or continuous signal is
obtained.
393
 Types of Flames
 Flames can be classified into several types depending on fuel/oxidant
used.

 The most common fuel-oxidizer combination is acetylene and air, which

produces a flame temperature of 2400–2700 K .

 If a hotter flame is required to atomize high boiling elements (called

refractory elements), acetylene and nitrous oxide are usually used.
Table 4A-3 Maximum flame temperatures

394
Flame Structure
 Interzonal region is the hottest part of the flame and best for atomic
absorption.
 Oxidation of the atoms occurs in the secondary combustion zone where
the atoms will form molecular oxides and are dispersed into the
surroundings.

Figure 4A-5 Temperature profiles in degrees

Figure 4A-4 Regions in a flame. celsius for a natural gas–air flame 395
396
 Burner
 Laminar-flow burners is common burner used in atomic spectrometry to
produce a relatively quiet flame and a long path length for maximizing
absorption.

Figure 4A-6 A laminar-flow burner. 397

2. Electrothermal atomization
 The sample is contained in a heated graphite furnace, by passing an
electrical current through it (thus, it is electrothermal)

 It is more sensitive than flames because it confines atomized sample in

the optical path for several seconds and requires less sample (1-100 µL).

 Ar gas is passed over the furnace to prevent oxidation of the graphite.

 A few sample are injected into the atomization chamber (a cylinder of

graphite coated with a film of pyrolytic carbon) where the following
processes take place
398
 The following processes take place using the electrothermal atomization

 Evaporation: the solvent associated with the sample is evaporated in a

low temperature (~120 °C) slow process (seconds).

 Ashing: sample is ashed to burn organics associated with the sample at

moderate temperatures (~600 °C, seconds).

 Atomization: The current is rapidly increased after ashing so that a

temperature in the range from 2000-3000 °C is obtained in less than 1
second.

399
 It is used for atomic absorption and atomic fluorescence measurements
but have not been applied for direct production of emission spectra.

 They are also used for vaporizing samples in inductively coupled plasma
emission spectroscopy.

Figure 4A-7 Cross-sectional view of a graphite furnace.

400
Advantages of the graphite furnace :
(1) small sample volumes are needed, and
(2) the sensitivity is substantially increased.
 Atomization in this furnace is nearly 100% efficient which is a
tremendous improvement over the flame
 Detection limits are improved by as much as 1000 times.

The major disadvantages:

(1) there often can be matrix and background absorption effects,
(2) reproducibility is not as good as with flames.

 Standard additions can be a solution to the matrix effect.

401
3. Inductively Coupled Plasmas
 involves use of high temperature plasma for sample
atomization/excitation.

 Higher fraction of atoms exist in the excited state, giving rise to an

increase in emission signal and allowing more types of atoms to be
detected

 The high temperature, stability, and relatively inert Ar environment

eliminate much of the interference encountered with flames. .

 Allow simultaneous multielement analysis.

 Plasma is normally used for emission, not absorption, because it is so hot

that there is a substantial population of excited-state atoms and ions 402
 Ions forced to
flow in closed
path, Resistance
Magnetic
to flow causes
field
heating Temperature Regions
in Plasma Torch

403
 Effects of temperature on atomic spectra
 Temperature determines the
degree to which a sample breaks down into atoms and
the extent to which a given atom is found in its ground, excited, or
ionized states.

The Boltzmann Distribution

 Consider an atom with energy levels E0 and E* separated by ΔE

Figure 4A-8 Two energy levels with different degeneracies

404
 The Boltzmann distribution describes the relative populations of
different states at thermal equilibrium.

 If equilibrium exists, the relative population (N*/N0) of any two states is

where T is temperature (K) and k is Boltzmann’s constant (1.381 x 10-23

J/K).

405
 Example: The lowest excited state of a sodium atom lies 3.371 x 10-19
J/atom above the ground state. The degeneracy of the excited state is 2,
whereas that of the ground state is 1. What is the fraction of Na in the
excited state in an acetylene-air flame at 2600 K is

 That is, less than 0.02% of the atoms are in the excited state.
 If the temperature were 2610 K, fraction of atoms in the excited state is

 The fraction of atoms in the excited state is still less than 0.02%, but that
fraction has increased by 100(1.74 - 1.67)/1.67 = 4%
406
 Absorption arises from ground-state atoms, but emission arises from
excited-state atoms.

 Absorption methods are theoretically less dependent on temperature

because measurements are made on initially unexcited atoms.

 Varying the temperature by 10 K hardly affects the ground-state

population and would not noticeably affect the signal in atomic
absorption.

 However, because the excited state population changes by 4% when the

temperature rises 10 K, emission intensity rises by 4%.

 Thus, an analytical method based on the measurement of atomic

emission requires close control of atomization temperature.
407
Atomic Absorption Spectroscopy
(AAS)

408
 AAS is a spectroanalytical procedure for qualitative & quantitative
analysis of chemical elements based on absorption of optical radiation
(light) by free atoms in the gaseous state.

 AAS is used to determine over 70 different elements in solution

409
 AAS makes use of absorption spectrometry to assess the conc. of an
analyte sample in solution.

 It requires standards with known analyte content to establish the relation

between the measured A and the analyte conc. and this relies therefore
on the Beer-Lambert Law.

 In short, the e’s of atoms in the atomizer can be promoted to higher

orbitals (ES) for a short period of time (nanoseconds) by absorbing a
defined quantity of radiant energy of a given ).

 This amount of energy, i.e., , is specific to a particular electron transition

in a particular element.
410
 Flame Atomic Absorption Spectroscopy (FAAS)
Sequence of events occur in flame atomization process
Na+ (aq) + Cl- (aq) (Solution
Nebulization ↓
Na+ (aq) + Cl- (aq) (Aerosol)
Loss of water ↓
NaCl (Solid)
Melting ↓
NaCl (liquid)
Vaporization ↓
NaCl (gas)
Atomization ↓
Na0 (gas) + Cl0 (gas)
Excitation by Heat/lamp ↓ Absorption of energy (AAS)
Na* (gas)
↓ Emission of energy/Fluorescence(AES/AFS)
Na0 (gas)
411
 Instrumentation

Figure 4A-9: Schematic Diagram of an Atomic-Absorption Spectrotometer

412
Figure 4A-10: Block Diagram of an Atomic-Absorption Spectrometer 413
 Flame Atomic Absorption spectrometry

atomizer

Figure 4A-10: Block Diagram of an Flame Atomic-Absorption Spectrotometer

414
A. Light source
 The light source, in FAAS can be either
(a) The Hollow Cathode Lamp (HCL) or
(b) Electrodeless Discharge Lamp (EDL).
(a) The Hollow Cathode Lamp (HCL)
 It consists of a
 Cathode made of analyte metal or serves as a support for a coating
of analyte metal of interest

 Anode tungsten enclosed in a borosilicate quartz envelope which

contains an inert gas at a pressure of about 1 to 5 torr
 Application of high potential across the electrodes causes a discharge which
creates ions of noble gas.

 These ions are accelerated to the cathode, which on collision dislodge

(sputtering) some of the metal atoms. 415
 Hollow cathode lamp (HCL)

Cathode: in the form of a cylinder, made of the element being studied

in the flame
Anode: tungsten 416
 Light emitted by hallow-cathode lamp has the same wavelength as the
light absorbed by the analyte element.

 Different lamp required for each element (some are multi-element)

417
(b) Electrodeless Discharge Lamp (EDL)
 An EDL is sometimes used as the light source in place of HCL

 Here, there is no anode or cathode; rather a small, sealed quartz tube

containing the metal or metal salt and some argon at low pressure is
wrapped with a coil for the purpose of creating a radio frequency (RF)
field.

 The tube is thus inductively coupled to an RF field and the coupled

energy ionizes the argon.

 The generated electrons collide with the metal atoms, raising them to the
ES.

 EDL’s are available for 17 different elements

418
Free electrons (e-) in EDL are
accelerated by microwave field.

Accelerated electrons collide with the

argon atoms (Ar) and ionize (Ar+) or
excite (Ar*) them.

Excited argon atoms (Ar*) collide with

mercury atoms to form exciting states
(Hg*), which emit energy (hv) as
UV/VIS radiation at return to ground
state (Hg).
419
C. Monochromator
 The monochromator is used to isolate the resonance line from all the
non-absorbed lines emitted by the radiation source.

 Prisms and gratings are generally used for monochromatization.

420
D. Detectors
 The detector is normally a photomultiplier tube, which produces an
electrical current dependent on the light intensity.

 The electrical current from the Photomultiplier tube is then amplified

and processed by the instrument electronics to produce signal which is
a measure of the light attenuation occurring in the sample cell.

421
 Flame atomic absorption is very convenient & widespread, it has an
acceptable level of accuracy for most analytes.

 However, there are limitations with the use of flames as atomizers

compared to other atomizers recently invented:

 First, flames require relatively large sample volumes (at least

several mL).

 Second, flames produce fewer atoms in the path of the light,

making them less sensitive.

 Third, flames are not applicable to samples in certain matrices, due

to undesirable matrix effects.
422
 Therefore, other types of atomizers are often required for better sensitivity
& more control over the chemical environment of the analyte; some of
these are discussed as follow.
A. The cold vapor mercury technique
B. Hydride generation technique
C. Graphite furnace atomic absorption

423
A) The cold vapor mercury technique
 The cold vapor method is only used for
the determination of mercury.

 The Hg salts is converted to Hg vapor by

using a strong acidic reducing agent such
as Tin (SnCl2) and HCl or NaBH4 and HCl
:

3H2O + 2NaBH4 + HCl → 8H + 2H3BO3

8H + Hg+2 = Hg0 + 3H2

 The detection limit for mercury by this cold

vapor technique is approximately 0.02
mg/L. 424
424
B) Hydride generation technique (HGAAS)
 Here, the hydrides generated must be
heated in air/acetylene flame or
electrically to create atoms in the free
state.

 The volatile hydrides are then carried

to a sampling cell in the light path of
the AA spectrometer.

 To dissociate the hydride gas into free

atoms, the sample cell must be
heated.
 It is another alternative technique for difficult elements like As, Bi, Ge, Pb, Sb, Se,
Sn, and Te
425
C) Graphite furnace technique
 The graphite furnace is an electrothermal
atomiser system that can produce
temperatures as high as 3000 °C.

 The heated graphite furnace provides the

thermal energy to break chemical bonds
within the sample and produce free ground
state atoms.

 Ground-state atoms then are capable of

absorbing energy, in the form of light, and
are elevated to an excited state.

 The amount of light energy absorbed

increases as the concentration of the
selected element increases. 426
 Calibration and Analysis
 Spectroscopic techniques require calibration with standards of known
analyte concentration.

 Calibration curves can be obtained by plotting absorbance (for AAS),

emission signal (for AES), fluorescence signal (for AFS) against
concentration

 The instrument is calibrated using several solutions of known

concentrations.

 The absorbance of each known solution is measured and then a

calibration curve of concentration vs absorbance is plotted.

 The unknown concentration of the element is then calculated from the

calibration curve 427
 Calibration curve
C (mg/L) Abs y = 0.008x + 0.1397
A 1.0 - Unknown 0.79 R² = 0.9927
b 0.9 -
S 0.8 - * C (mg/L) Abs
o 0.7 - *
r 0.6 - * 23 0.34
b 0.5 - * 37 0.42
a 0.4 - * 48 0.52
n 0.3 - * 63 0.64
c 0.2 -
e 0.1 -
72 0.73

10 20 30 40 50 60 70 80 90 100
Concentration ( mg/L )
428
 Interferences in AAS
 Interference is any effect that changes the signal while analyte
concentration remains unchanged.

 Interference can be corrected by removing the source of interference or

by preparing standards that exhibit the same interference.

 Interferences of two types are encountered in atomic absorption

methods.
Spectral Interference.
Chemical Interference

429
A. Spectral interferences
 It refers to the overlap of analyte signal with signals due to other
elements or molecules in the sample or with signals due to the flame or
furnace that the monochromator cannot resolve them.

Solution
 The best solution is choosing altenative wavelength for analysis.
 Example: V line is 308.2 nm and Al line is at 308.2 nm.
Choose a different Al line at 309.2 nm.

 High-resolution spectrometers eliminate interference from other elements

by resolving closely spaced lines.
430
B. Chemical interferences
 It is caused by any component of the sample that decreases the extent
of atomization of analyte.

 Elements that form very stable compounds are said to be refractory

because they are not completely atomize at the temperature of the flame
or furnace.

 Solution
 Use a higher flame temperature (nitrous oxide/acetylene)
 Use a releasing agent
 Use protective chelation

431
 Determination of calcium in the presence of sulfate or phosphate (e.g. in
natural waters)
3Ca2+ + 2PO43- → Ca3(PO4)2 (stable compound)

Releasing agent
Add 1000 ppm of LaCl3
2LaCl3 + Ca3(PO4)2 → 3CaCl2 + 2La(PO4)
CaCl2 readily dissociates

Protective chelation
Ca3(PO4)2 + 3EDTA → 3Ca(EDTA) + 2PO43-
Ca(EDTA) dissociates readily.
432
Ionization interferences
 Ionization interference can be also a problem in the analysis of alkali
metals at relatively low temperature because they have low ionization
potentials.
M(g)  M+(g) + e-

 Example: sodium is 5% ionized and potassium is 33% ionized.

 Ions have energy levels different from those of neutral atoms, so the
desired signal is decreased.

433
Solution
 Add an ionisation suppressor which are easily ionised element such as
Cs.

 An ionization suppressor decreases the extent of ionization of analyte.

 Example: For analysis of potassium, 1000 ppm of CsCl is added,

because cesium is more easily ionized than potassium.

 By producing a high concentration of electrons in the flame, ionization of

Cs suppresses ionization of K.

 The method of standard addition compensates for many types of

interference by adding known quantities of analyte to the unknown in its
complex matrix. 434
 Applications of AAS
 Water and effluents
many elements e.g. Ca, Mg, Fe, Si, Al, Ba
 Food and Medicines
wide range of elements
 Animal feedstuffs
Mn, Fe, Co, Cu, Zn, Cr, Se
 Agricultural analysis
 soils
 Plants
 Clinical and biochemistry
 whole blood, plasma and serum Ca, Mg, Li, Na, K, Cu, Zn, Fe etc.
 Metallurgy
 Ores, metals and alloys
435
Atomic Emission Spectroscopy
(AES)

436
 Atomic emission spectroscopy measures radiation emitted when valence
electron in a higher energy atomic orbital returns to a lower energy.

 It uses quantitative measurement of the emission from excited atoms to

determine analyte concentration.

 The intensity of an atomic emission line, Ie, is proportional to the number

of atoms, N*, populating the excited state.
Ie=kN∗

 If a system of atoms is in thermal equilibrium, the population of excited

state i is related to the total concentration of atoms, N, by the Boltzmann
distribution.

437
 Instrumentation
 The instrumentation of atomic emission spectroscopy is the same as that
of atomic absorption, but without the presence of a radiation source.

 In atomic emission the sample is atomized and the analyte atoms are
excited to higher energy levels all in the atomizer.

Figure 4B-1 Schematic Diagram of an Atomic Emission spectrometer

438
 Emission spectrometry atomization and sources

 The flame (1700 – 3150 oC) is most useful for elements with relatively
low excitation energies like sodium, potassium and calcium .

 The plasma (6000 – 8000 oC) has a very high temperature and is useful
for elements of high excitation energies.

439
 Emission spectrometry atomization and sources
Plasma sources
 A plasma is a hot, partially ionized gas that contains an abundant
concentration of cations and electrons.

 The plasmas used in atomic emission are formed by ionizing a flowing

stream of argon gas, producing argon ions and electrons.

 A plasma’s high temperature results from resistive heating as the

electrons and argon ions move through the gas.

 Because plasmas operate at much higher temperatures than flames,

they provide better atomization and a higher population of excited states.

 Such plasmas achieve temperatures as high as 10,000 K.

440
 There are different plasma sources
 Inductively coupled plasma (ICP)
 Direct current plasma (DCP)
 Microwave induced plasma (MIP)
 Laser-induced plasma,
 Laser-induced breakdown(LIBS)

441
Inductively Coupled Plasma Source
 The ICP torch consists of three concentric
quartz tubes, surrounded at the top by a
radio-frequency induction coil.

 The sample is mixed with a stream of Ar

using a nebulizer, and is carried to the plasma
through the torch’s central capillary tube.

 Plasma formation is initiated by a spark from

a Tesla coil.

 RF produces fluctuating magnetic field that

induces the argon ions and the electrons to
move in a circular path. 442
Mechanism of plasma formation
 The ionisation of the argon gas flowing through the crystal tube inside
the solenoid is initiated by a spark from a Tesla coil.

 The resulting ions and the electrons are subjected to the fluctuating
magnetic field produced by the induction coil and flow in the closed
annular paths within the coils.

 These electrons rapidly acquire enough energy from the oscillatory field
generated by the induction coil and sustain a high degree of ionisation.

 This leads to the formation of ring shaped toroidal plasma.

 The spacing between coil and torch, the distance between individual
copper coils and the concentricity of both coil and torch are important
parameters in the formation of stable plasma.
443
Figure 3B-2 Schematic diagram of an inductively coupled plasma torch.

444
 Instrumentation for ICP-AES

Figure 4B-6 : A schematic layout of different components of an ICP-AES spectrometer

445
Quantitative Analysis using ICP-AES
Example: 10-g portion of the salt substitute is dissolved in 10 mL of 3 M HCl and
100 mL of distilled water and diluted to a 250-mL. A series of standard additions is
prepared by placing 25-mL portions of the diluted sample into separate 50-mL
volumetric flasks, spiking each with a known amount of an approximately 10 mg/L
standard solution of Na+, and diluting to volume. The emission intensity is
measured for each of the standard addition. The results of a flame atomic emission
analysis of the standards is

added Na (μg/mL) Ie (arb. units)

0 1.79
0.42 2.63
1.051 3.54
2.102 4.94
3.153 6.18
What is the concentration of sodium, in μg/g, in the salt substitute? 446
Solution
The concentration of sodium in the
sample is equal to the absolute value of
the calibration curve’s x-intercept.
Substituting zero for the emission
intensity and solving for sodium’s
concentration gives a result of 1.44
μg/mL Na. The concentration of sodium
in the salt substitute is

447
 Advantages of ICP-AES
 The wide applicability of ICP-AES in the quantitative analysis of various
materials can be attributed to the following advantages
 Rapid and simultaneous multi-element analysis.
 Lack of chemical interferences.
 High temperature of the excitation source : 5000 to 10000K.
 Low sample requirements.
 Low detection limits: 1 to 100 ng/g or µg/l (part per billion).
 Good accuracy and precision: relative standard deviation of about
1 per cent.
 Applicability to elements that are difficult to be determined by AAS:
B, C, Ce, La, Nb, Pr, S, P, Ti, Ta, V and Zr can also be measured. .
448
 Applications of ICP-AES
 The ICP-AES technique is versatile tool in the hands of analytical chemists.

 Agricultural science:
 Analysis of agricultural products and foods besides soil analysis.
 Health sciences
 Determination of Al in blood, Cu in brain tissue, Se in liver, Na in
breast milk.
 Direct determination of Ca, Fe, Cu, Mg, Na and K in serum samples.
 Geological sciences
 Presence of lanthanides and other elements in rock samples.
 Forensic Sciences
 Crime scene soil analysis.
449
 Forensic Sciences
 Crime scene soil analysis.
 Metallurgy
 Analysis of trace elements in stainless steel.
 Environmental science
 Waste water analysis, determination of pollutant metals in variety of
matrices.
 Industry
 Presence of metals like Cu, Fe, Ni, and Si in lubricating oils or gasoline
at tracer concentration.
 Traces of metals like Ca, Cu, Fe, Mn, Mg, P, K and Zn in beer or wine;
determination of trace elements in polymers, evaluation of catalysts,
and so on.
450