Chapter 1

Introduction to Spectroscopy

Ephrem Tilahun (MSc., Ass.Prof)

Jimma University
E.T 1
• Spectroscopy is the study of the interaction
between radiation (electromagnetic radiation or
light, as well as particle radiation) and matter.
• Spectrometry is the measurement of these
interactions
• instrument which performs such measurement
– spectrometer or
– spectrograph.
• A plot of the interaction is referred to as a
– spectrum

E.T 2
 Classification of spectroscopic methods
• Nature of radiation measured
• The type of spectroscopy depends on the physical quantity
measured.
• Normally, the quantity that is measured is an amount or intensity of
something.
• Electromagnetic spectroscopy involves interactions with
electromagnetic radiation, or light.
– Ultraviolet-visible spectroscopy is an example.
• Electronic spectroscopy involves interactions with electron beams.
– Auger spectroscopy involves inducing the Auger effect with an
electron beam.
• Mechanical spectroscopy involves interactions with macroscopic
vibrations, such as phonons.
– An example is acoustic spectroscopy, involving sound waves.
• Mass spectroscopy involves the interaction of charged species with
magnetic and/or electric fields, giving rise to a mass spectrum.

E.T 3
• Measurement process
• Most spectroscopic methods are differentiated as either atomic or
molecular based on whether or not they apply to atoms or molecules.
• Along with that distinction, they can be classified on the nature of their
interaction:
• Absorption spectroscopy uses the range of the electromagnetic spectra in
which a substance absorbs.
– atomic absorption spectroscopy and
– various molecular techniques, such as infrared spectroscopy in that region a
– nuclear magnetic resonance (NMR) spectroscopy in the radio region.
• Emission spectroscopy uses the range of electromagnetic spectra in which
a substance radiates (emits).
– luminescence.
– Molecular luminescence techniques include spectrofluorimetry.
• Scattering spectroscopy measures the amount of light that a substance
scatters at certain wavelengths, incident angles, and polarization angles.
– The scattering process is much faster than the absorption/emission process.
• Raman spectroscopy

E.T 4
 Electromagnetic radiation
• EMR, or light, is a form of energy whose behaviour is
described by the properties of both waves and particles.
• The optical properties of electromagnetic radiation, such
as diffraction, are explained best by describing light as a
wave.
• Many of the interactions between electromagnetic
radiation and matter, such as absorption and emission,
– however, are better described by treating light as a particle, or
photon.
• the dual models of wave and particle behaviour provide a
useful description for electromagnetic radiation

E.T 5
• Wave Properties of Electromagnetic Radiation
• Electromagnetic radiation consists of oscillating
electric and magnetic fields that propagate
through space along a linear path and with a
constant velocity
• In a vacuum, electromagnetic radiation travels at
the speed of light, c, which is 2.99792 x108 m/s.
• Electromagnetic radiation moves through a
medium other than a vacuum with a velocity, v,
less than that of the speed of light in a vacuum.
• Oscillations in the electric and magnetic fields are
perpendicular to each other, and to the direction
of the wave’s propagation.
E.T 6
Figure shows an example of plane-polarized electromagnetic radiation consisting of
an oscillating electric field and an oscillating magnetic field, each of which is
constrained to a single plane. E.T 7
• The interaction of electromagnetic radiation with matter can be
explained using either the electric field or the magnetic field.
• For this reason, only the electric field component is shown in
Figure

E.T 8
• The oscillating electric field is described by a sine wave of the form
E = Ae sin(2πνt + Φ)

– where E is the magnitude of the electric field at time t, Ae is the electric field’s
maximum amplitude,
– v is the frequency, or the number of oscillations in the electric field per unit
time, and
– Φ is a phase angle accounting for the fact that the electric field’s magnitude
need not be zero at t = 0.
• An identical equation can be written for the magnetic field, M

M = Am sin(2πνt + Φ)

– where Am is the magnetic field’s maximum amplitude.

• only' the electrical vector is employed because it is the electrical force that
is responsible for such phenomena as transmission, reflection, refraction,
and absorption of radiation.
•  Magnetic responsible for the absorption of radio-frequency waves in
NMR

E.T 9
 Wave Parameters

• The time required for the passage of successive

maxima through a fixed point in space is called the
period (p )of the radiation.
• The frequency (v) is the number of oscillations of the
field that occurs per second and is equal to 1/p.
• Another parameter of interest is the wavelength λ,
which is the linear distance between any two equivalent
point on successive maxima or minima of a wave.
• Multiplication of the frequency in reciprocal seconds
by the wavelength in metres gives the velocity of
propagation
V= vλ
E.T 10
• It is important to realize that the frequency is
determined by the source and remains invariant
regardless of the media traversed by the radiation.
• In contrast, the velocity of propagation v, the rate
at' which the wave front moves through a
medium, is dependent upon both the medium and
the frequency;
 
• In a vacuum the velocity of radiation becomes
independent of frequency and is at its maximum.
• This velocity, given the symbol c, has been
accurately determined to be 2.99792 X 1010 cm/s.
Thus, for a vacuum,
• c= νλ = 3 x 1010 cm/s
E.T 11
• In any other medium, the rate of propagation is less because of interactions
between the electromagnetic field of the radiation and the bound electrons in
the atoms or molecules making up the medium.
• Since the radiant frequency is invariant and fixed by the source, the wavelength
must decrease as passes from a vacuum to a medium containing matter.

wave number, , which is the reciprocal of wavelength

E.T 12
• Particle Properties of Electromagnetic Radiation
• An understanding of certain interactions between radiation and
matter requires that the radiation be treated as packets of
energy called photons or quanta.
– The energy of a photon depends upon the frequency of the radiation,
and is given by

where h is Planck’s constant, which has a value of 6.626 x10 –34 J · s.

Photon : A particle of EMR having zero mass and an energy of hv.

E.T 13
Example 1:- The “D” line in the solar spectrum was due to the
absorption of solar radiation by sodium atoms. The wavelength of
the sodium D line is 589 nm. What are the frequency and the
wave number for this line?

SOLUTION
The frequency and wave number of the sodium D line are

E.T 14
Example 2:- What is the energy per photon of the sodium D line

(λ= 589 nm)?

SOLUTION
The energy of the sodium D line is

E.T 15
 Electromagnetic (EM) spectrum
• The electromagnetic (EM) spectrum is just a name that
scientists give a bunch of types of radiation when they
want to talk about them as a group.
• Radiation is energy that travels and spreads out as it
goes
– visible light that comes from a lamp in your house or
– radio waves that come from a radio station
• Other examples of EM radiation are microwaves,
infrared and ultraviolet light, X-rays and gamma-rays.
 

E.T 16
E.T 17
• I. Absorption of Radiation 
• When radiation passes through a transparent medium contain
chemical species, certain frequencies may be selectively
attenuate by the process of absorption.
• EMR energy is transferred to the atoms or molecules
constituting the sample; as a result, these particles are
promoted from a lower energy state to higher-energy states, or
excited states.
•  At room temperature, most substances are in their lowest
energy or ground state.
• Absorption then ordinarily involves a transition from the
ground state to higher-energy states.
• Atoms, molecules, or ions have only at limited number of
discrete, quantized energy levels;

E.T 18
• for absorption of radiation to occur, the energy
of the exciting photon must exactly match the
energy difference between the ground state and
one of the excited states of the absorbing
species.
• consider the three processes that may occur
when a two-state system is subjected to radiation
of frequency or wave number , corresponding to
the energy separation ∆E where

E.T 19
 1. Induced absorption, in which the molecular (or atom) M absorbs
a quantum of radiation and is excited from m to n:

Eg. the appearance of an aqueous solution of copper sulphate as blue

due to the absorption of the complementary colour, red, by the solution.
2. Spontaneous emission, in which M* (in state n) spontaneously
emits a quantum of radiation:

Eg. a sodium vapour or tungsten filament lamp, is of the

spontaneous type.
E.T 20
 3. Induced, or stimulated, emission.
This is a different type of emission process from that of type 2 in that
a quantum of radiation of wave number is required to induce,
or stimulate, M* to go from n to m.
The process is represented by

Since the energy d/n are unique for each species, a study of the
frequencies of absorbed radiation provides a means of characterizing
the constituents of a sample of matter.

For this purpose, a plot of absorbance as a function of wavelength or

frequency is experimentally derived absorption spectra

E.T 21
The general appearance of an absorption spectrum will depend upon
 the complexity,
 the physical state, and
 the environment of the absorbing species.
It is convenient to recognize two types of spectra, namely, those
associated with
 atomic absorption and
 those resulting from molecular absorption.
E.T 22
• A. Atomic Absorption
• When a beam of polychromatic Uv or Vis
radiation passes through a medium containing
gaseous atoms, only a few frequencies are
attenuated by absorption, and
• The spectrum consists of a number of very
narrow absorption lines

E.T 23
 5p

4p

3p
E
A

200 300 400 500 600

Wavelength, nm 3s

(a)Absorption spectrum for Na vapour (b) partial energy level diagram for Na
Transitions involves excitation of

the single outer electron of Na

E.T 24
• B. Molecular Absorption
• Molecules undergo three type of quantized transitions when
exited by UV, visible and IR radiation.
• For UV and VIS radiation excitation involves promoting an
electron from ground state (low energy molecular or atomic
orbital )to exited state (a higher – energy orbital).
• The energy hv of the photon must be exactly the same as the
energy d/n b/n the two orbital energies.
• The transition known as Electronic transition
– electronic absorption
• Molecules also exhibit two other types of radiation- induced
transitions
– Vibrational
– Rotational
•  

E.T 25
• For each electronic energy state of the molecule, there
normally exist several possible vibrational states, and for
each of these, in turn, numerous rotational states,

E.T 26
Vibrational transition come about b/c a molecule has a multitude of
quantized energy levels (vibrational state) associated with the bond that
holed the molecule together.

Symmetric Asymmetric

A)Stretching Vibrations

+ + + -

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

B) Bending vibrations
E.T 27
• Absorption by polyatomic molecules, particularly in the
condensed state, is a considerably more complex process
because the number of energy states is greatly enhanced.
• Here, the total energy of a molecule is given by
• E =Eele + Evib. + Erot.
– where Eele describes the electronic energy of the molecule, and
– Evib refers to the energy of the molecule resulting from various
atomic vibrations.
– The third term accounts for the energy associated with the
rotation of the molecule around its center of gravity.

E.T 28
Figure below is a graphical representation of the energies
associated with few of the electronic and vibrational states of a
molecule.

Fig.
E.T 29
• The heavy line labelled Eo represents the electronic
energy of the molecule in its ground state (its state of
lowest electronic energy);
• the lines labelled E1 and E2 represent the energies of
two excited electronic states.
• Several vibrational energy levels (0,1,…,4) are shown
for each of these electronic states.
• the energy difference between the ground state and an
electronically excited state is large relative to the
energy differences b/n vibration levels in a given
electronic state
– (typically, the two differ by a factor of 10 to 100).

E.T 30
• Visible radiation causes excitation of an electron from Eo to
any of the vibration levels associated with E 1'
• Ultraviolet causes excitation of an electron from Eo to any of
the vibration levels associated with E2
• Finally, the less energetic near- and mid infrared radiation can
only bring about transition among the vibrational levels of the
ground state.
• Although they are not shown, several rotational energy levels
are associated with each vibrational level.
• The energy difference between these is small relative to the
energy difference between vibrational levels;

E.T 31
In contrast to atomic absorption spectra, which consist of
a series of sharp, well-defined lines,

 Molecular spectra in the ultraviolet and visible regions are

ordinarily characterized by absorption bands
 that often encompass a substantial wavelength the spectrum for a
molecule ordinarily consists of a series of closely spaced
absorption bands, such as that shown for benzene vapor in Figure
below

E.T 32
Unless a high-resolution instrument is employed, the
individual bands may not be detected, and the spectra will
appear as smooth curves.

Finally, in the condensed state and in the presence of

solvent molecules, the individual bands tend to broaden to
give spectra such as those shown in the Figure below

E.T 33
• Pure vibrational absorption can be observed in the
infrared region.
– where the energy of radiation is insufficient to cause
electronic transitions.
• Variations in rotational levels may give rise to a
series of peaks for each vibrational state.
– However, rotation is often hindered or prevented in liquid
or solid samples;
– the effects of these small energy differences are
not ordinarily detected in such samples.

E.T 34
• Pure rotational spectra for gases can be observed in the
microwave region.
– Absorption Induced by a Magnetic Field.
• When electrons or the nuclei of certain elements are subjected
to a strong magnetic field additional quantized energy levels
are produced as a consequence of magnetic properties of these
elementary particles.
– Absorption by nuclei or by electrons in magnetic fields is studied by
nuclear magnetic resonance (NMR) and
– electron spin resonance (ESR) techniques, respectively
 

E.T 35
 Relaxation Processes
• Ordinarily, the lifetime of an atom or molecule
excited by absorption of radiation is short because
several relaxation processes exist which permit its
return to the ground state.
• Two of the most important of these mechanisms
• nonradiative relaxation
• fluorescent relaxation

E.T 36
Fig. 5
E.T 37
• Two type of nonradiative relaxation are shown in the figure 5b Vibrational
deactivation or relaxation,
– denoted by short arrows b/n vibrational energy levels,
– involves the loss of energy in a series of small steps,
– the excitation energy being converted to kinetic energy by collision with solvent molecules.
• These energy transferd to solvent molecule and reflacted by a tiny increase in the
temperature of the medium.
• Non radiative relaxation b/n the lowest vibrational level of an exited electronic
state and the upper vibrational level of another electronic level can also occur.
– Represent by long arrow.
• Less efficient than vibrational relaxation and its life time is b/n 10 -6 and 10-9 
• As shown in Figure 5c, relaxation can also occur by emission of fluorescent
radiation.
 

E.T 38
 II. Emission Radiation
 
• Excited particles (ions, atoms, or molecules)can be excited to
one or more higher energy levels  by a variety of means,
including
– bombardment with electrons or other elementary particles,
– exposure to a high-potential alternating current spark,
– heat treatment in an arc or a flame, or
– absorption of electromagnetic radiation.
• The lifetime of an excited species is generally transitory (10 -6 –
10-9 s) and
• a relaxation to a lower-energy levels or to their ground states
takes place with the release of the excess energy in the form of
Electromagnetic radiation, heat or perhaps both.

E.T 39
• Emission spectra
• A plot of the relative power of the emitted radiation as a
function of wavelength or frequency.

Figure 6 Emission spectrum of a brine sample obtained with an oxyhydrogen flame. The spectrum
consists of the superimposed line. band. and continuum spectra of the constituents of the sample. The character-
istic wavelengths of the species contributing to the spectrum are listed beside each feature. (R. Hermann and
C. T. J. Alkemade, Chemical Analysis by Flame Photometry,E.T2nd ed.. p. 484. New York: Interscience, 1979 .) 40
• There are three type of spectra:- line, band and continues.
•   Excitation can be brought about Radiating particles that
are well separated from one another, as in the gaseous
state, behave as independent bodies and often produce
radiation containing relatively few specific wavelengths.
• The resulting spectrum is then discontinuous and is
termed a line spectrum.
• Made up of a series of sharp, well-defined peaks caused
by an excitation of individual atom. 
• In fig. 6 lines for Na, K, Sr and Ca

E.T 41
• The band spectrum consists of several groups of lines so closely spaced that they
are not completely resolved.
– The source of the band is small molecules or radicals 
– In fig.6 bands of OH,MgOH and MgO
• Bands arise from the numerous quantized vibrational levels that are superimposed
on the ground state electronic energy level of a molecule.
• A continuous spectrum, on the other hand, is one in which all wavelengths are
represented over an appreciable range, or one in which the individual wavelengths
are so closely spaced that resolution is not feasible by ordinary means.
– The line and band spectra are superimposed
• Continuous spectra result from excitation of:
• (1) solids or liquids, in which the atoms are so closely packed as to be incapable of
independent behaviour; or
• (2) complicated molecules possessing many closely related energy states.

E.T 42
• When solids are heated to incandescence, the continuous
radiation that is emitted is more characteristic of the
temperature of the emitting surface than of the material of
which that surface is composed.
• Radiation of this kind (called black-body radiation)
• is produced by the innumerable atomic and molecular
oscillations excited in the condensed solid by the thermal
energy.

Figure 7 Blackbody radiation curves for various light sources. Note the shift in the peaks as the temperature of the
sources changes. E.T 43
• Both continuous spectra and line spectra are of
importance in analytical chemistry.
• The former are frequently employed in
methods based on the interaction of radiation
with matter, such as spectrophotometry.
• Line spectra, on the other hand, are important
because
• they permit the identification and determination of the
emitting species.
E.T 44
Absorption Law
Chapter 2

E.T 45
 The absorption law
• also known as the Beer-Lambert law or just
Beer's law,
• Tells us quantitatively how the amount of
attenuation depends on the concentration of
the absorbing molecules and the path length
over which absorption occurs.
• As light traverses a medium containing an
absorbing analyte, decreases in intensity occur
as the analyte becomes excited.

E.T 46
 Transmittance and Absorbance
• The common terms and alternative names/symbols
employed in spectroscopy are listed in the table
below. The recommended terms and symbols are
listed under the column labeled Term and Symbol.

E.T 47
Terms and Symbols

E.T 48
 Transmittance
Figure 1 depicts a beam of parallel radiation before and after it has passed
through a layer of solution with a thickness of b cm and a concentration of c of
an absorbing species.
As a consequence of interactions between the photons and absorbing particles,
the power of the beam is attenuated from Po to P.
The transmittance T of the solution is the fraction

Equ.1

E.T 49
 Absorbance
• Absorbance, like the previous table shows, can
be defined as the base-ten logarithm of the
reciprocal of the transmittance :
A = log 1/T = -log I/Io = -log P/Po Equ.2

E.T 50
• Absorptivity and Molar Absorptivity
• Absorbance is directly proportional to the path length
through the solution and the concentration of the
absorbing species.
– That is, A = abc
• where a is a proportionality constant called
– the absorptivity.
• The magnitude will clearly depend upon the units used for
b(cm) and c (g/L).
• When the concentration is expressed in moles per litter
and the cell length is in centimetres,
– the absorptivity is called the molar absorptivity and given the
special symbol ԑ
– A = ԑbc

E.T 51
 Experimental Measurements of Absorbance and
transmittance
 
• The relationship given by Equation 1 and 2 is not directly
applicable to chemical analysis.
• Neither Absorbance nor Transmittance, as defined, can be
conveniently measured in the laboratory
– because the solution to be studied must be held in some sort of
container.
• Interaction between the radiation and the walls is inevitable
leading to a loss by reflection at each interface;
• significant absorption may occur within the walls themselves.
• the beam may suffer a diminution in power during its passage
through the solution as a result of scattering by large
molecules or inhomogeneities.
E.T 52
Reflection and Scattering Losses

E.T 53
Reflection and Scattering Losses (cont)
• Reflection and scattering losses are significant and to
compensate for these effects, the power of the beam
transmitted by the analyte solution is ordinarily
compared with the power of the beam transmitted by
an identical cell containing only the solvent.
• An experimental absorbance that closely
approximates the true absorbance is then obtained
with the equation:
A = log Psolvent/Psolution ≈ log Po/P

E.T 54
• Example:
• A sample in a 1.0 cm cell is determined with a
spectrometer to transmit 80 % light at a certain
wavelength. If the absorptivity of this substance at
this wavelength is 2.0, what is the concentration of
the substance?
• Solution:
• The percent transmittance is 80 % and so T = 0.80:
1
log  2.0 cm -1 g 1 L 1.0 cm  c
0.80
log1.25  2.0 g L  c-1

0.10
c  0.050 g / L
2.0 E.T 55
 Example:
A solution containing 1.00 mg ion (as the thiocyanate complex) in 100 mL
was
observed to transmit 70.0% of incident light compared to an appropriate
blank.
(a) What is the absorbance of the solution at this wavelength?
(b) What fraction of light would be transmitted by a solution of iron four
times as concentrated?
Solution: T  0.70
1
A  log  log1.43  0.155
0.70
0.155  ab(0.0100 g / L)

ab  15.5 L / g
Therefor A  15.5 L/g (4  0.0100 g/L) = 0.620
e, 1
log  0.620
T
T  0.240
A1 abc1 c1
he absorbance of the new solution could have  
een calculated more directly: A2 abc2 c2
c 4
E.T A2  A1  2  0.155   0.620 56
c1 1
 Beer’s Law
Consider This:
• A parallel beam of
monochromatic radiation
with power Po strikes the
block perpendicular to a
surface after passing
through a length b of the
material , which contains
n absorbing particles , the
beam’s power is decreased
to P as a result of
absorption.

E.T 57
 area S and an infinitesimal thickness dx.
Within this section there are dn absorbing
particles;
associated with each particle, we can imagine a
surface
at which photon capture will occur.
That is, if a photon reaches one of these areas by

chance, absorption will follow immediately.

 The total projected area of these capture
surfaces
within the section is designated as dS;
the ratio of the capture area to the total area,
then, is
dS/S.
 On a statistical average,
E.T this ratio represents the
58
 The power of the beam entering the section, Px, is
proportional to the number of photons per square
centimeter per second, and
 dPx represents the quantity removed per second
within the section;
 the fraction absorbed is then - dPx /Px, and this
ratio also equals the average probability for
capture.
 The term is given a minus sign to indicate that P
undergoes a decrease. Thus,

eq.3

E.T 59
Recall, now, that dS is the sum of the capture areas for particles within the
section; it must therefore be proportional to the number of particles, or
eq. 4

where dn is the number of particles and a is a proportionality

constant, which can be called the capture cross section
Combining Equations 3 and 4 and summing over the interval
between zero and n, we obtain

eq 5

Integration gives
eq 6

E.T 60
 converting to base 10 logarithms and inverting the fraction to
change the sign, we obtain

eq 7

where n is the total number of particles within the block shown in Figure 2. The
cross sectional area S can be expressed in terms of the volume of the block V
and its length b.
Thus,
eq. 8

Substitution of this quantity into Equation 7 yields

E.T 61
Note that n/V has the units of concentration (that is, number of particles per
cubic centimetre); we can readily convert n/V to moles per litter. Thus, number
of moles given by

and c in mol/L is given by

eq.9

Combining eq.8 and 9

E.T 62
Finally, the constants in this equation can be collected into a
single term ԑ to give

which is Beer's law.

E.T 63
 Application of Beer`s Law to
Mixture
• Beer's law also applies to a solution containing more than one
kind of absorbing substance.
• Provided there is no interaction among the various species,
the total absorbance for a multicomponent system is given by
Atotal = A1 + A2 + ... + An (6-11) = ԑ1bcl + ԑ2bc2 + ... + ԑnbcn
• where the subscripts refer to absorbing components 1, 2, ..., n.

E.T 64
 Deviations from Beer’s Law
• Beer’s law states that a plot of absorbance versus
concentration should give a straight line passing
through the origin with a slope equal to ab. However,
deviations from direct proportionality between
absorbance and concentration are sometimes
encountered.
• These deviations are a result of one or more of the
following three things ; real limitations, instrumental
factors or chemical factors.

E.T 65
 Real Limitations
• Beer’s law is successful in describing the absorption
behavior of dilute solutions only ; in this sense it is a
limiting law. At high concentrations ( > 0.01M ),the
average distance between the species responsible for
absorption is diminished to the point where each affects
the charge distribution of its neighbors.
• This interaction, in turn, can alter the species’ ability to
absorb at a given wavelength of radiation
– Because the extent of interaction depends upon concentration,
• the occurrence of this phenomenon thus leading to a
deviation from Beer’s law.

E.T 66
 Limitations (cont)
• A similar effect is sometimes encountered in solutions
containing low absorber concentrations and high
concentrations of other species, particularly electrolytes.
• The close proximity of ions to the absorber alters the molar
absorptivity of the latter by electrostatic interactions;
– the effect is lessened by dilution
• Deviations also arise because ԑ is dependent upon the
refractive index of the solution. Thus, if concentration
changes cause significant alterations in the refractive index µ
of a solution, departures from Beer’s law are observed.

E.T 67
 Chemical Deviations
• Apparent deviations from Beer's law are frequently
encountered as a consequence of association,
dissociation, or reaction of the absorbing species with
the solvent to generate a product that has a different
absorption spectrum with the analyte.
• A common example of this behavior is found with
acid/base indicators.
• Deviations arising from chemical factors can only be
observed when concentrations are changed.

E.T 68
 Instrumental Deviations
• Unsatisfactory performance of an instrument
may be caused by fluctuations in the power-
supply voltage, an unstable light source, or a
non-linear response of the detector-amplifier
system.

E.T 69
 Polychromatic Radiation
• Strict adherence to Beer’s law is observed only with truly
monochromatic radiation. This sort of radiation is only
approached in specialized line emission sources.
• All monochromators, regardless of quality and size, have a
finite resolving power and therefore minimum
instrumental bandwidth.
• the use of radiation that is restricted to a single wavelength
is seldom practical; devices that isolate portions of the
output from a continuous source produce a more or less
symmetric band of wavelengths around the desired one

E.T 70
 Polychromatic Radiation (cont)
• A good picture of the effect of polychromatic
radiation can be presented as follows. When radiation
consists of two wavelengths, λ’ and λ’’, and assuming
that Beer’s law applies at each of these individually
• the absorbance at λ’ is given by:
log ( P’o/P’ ) = A’ = ԑ’bc
P’o /P’ = 10ԑ’bc
P’ = p’0 10-ԑ’bc

Similarly at λ’’ is given by P’’ = p0’’ 10-ԑ’’bc

E.T 71
 When an absorbance measurement is made with radiation composed of both
wavelengths, the power of the beam emerging from the solution is given by (P' +
P") and that of the beam from the solvent by (P’O + P’’O).
Therefore, the measured absorbance is

E.T 72
E.T 73
• If the two molar absorpitivities differ, however, the
relationship between AM and concentration will no longer be
linear; moreover, greater departures from linearity can be
expected with increasing differences between ԑ' and ԑ`'.

FIGURE the effect of polychromatic radiation on beer’s law. In the spectrum at the left, the
absorptivity of the analyte is nearly constant over band A from the source. Note in the beer’s law
plot at the right that using band A gives a linear relationship. In the spectrum, band B corresponds
to a region where the absorptivity shows substantial changes. In the right plot, note the dramatic
deviation from beer’s law that results.

E.T 74
 Chapter Three

Instruments for optical spectroscopy

E.T 75
• The basic components of analytical instruments
– for emission,
– absorption and
– fluorescence spectroscopy
• Are remarkably alike in function and general
performance requirements regardless of whether
the instrument are designed for Uv, Vis or IR
radiation.
• Called Optical instruments

E.T 76
• Spectroscopic instruments contain five
components, including:
• a stable source of radiant energy;
• a wavelength selector that permits the isolation
of a restricted wavelength region;
• a transparent container for holding the sample;
• a radiation detector or transducer, that converts
radiant energy to a usable signal (usually
electrical); and
• a signal processor and readout
E.T 77
FIGURE 1 Components for various types of instruments for
optical spectroscopy: (a) absorption spectroscopy,
(b), fluorescence and scattering Spectroscopy
E.T
and (c) emission spectroscopy 78
• As can be seen in the figure, the configuration of components
(4) and (5) is the same for each type of instruments. 
• Emission spectroscopy differ from the other two types in that
components 1 & 3are combined,
– that no external radiation source is required;
• the sample itself is the emitter.
– the sample is usually fed into a plasma or a flame, which provides enough
thermal energy to cause the analyte to emit characteristic radiation..
• Absorption and fluorescence spectroscopy require an external source of
radiant energy and a cell to hold the sample.
• For the absorption measurements
• The beam from the source passes through the sample after leaving the
wavelength selector.
• In fluorescence Here, two wavelength selectors are needed to select the
excitation and emission wavelengths. The selected source radiation is
incident on the sample and the radiation emitted is measured. usually at
right angles to avoid scattering.

E.T 79
Optical Material
The cell, windows, lenses and wavelength – selecting elements
in a optical spectroscopy instrument must transmit radiation in the
wavelength region being investigated.

Figure 2a Transmittance ranges for various construction materials.

E.T 80
Figure 2b Transmittance ranges for wavelength selectors

E.T 81
• Ordinary silicate glass is completely adequate for use
in the visible region and has the considerable
advantage of low cost.
• In the UV region at wavelengths shorter than about
380 nm glass begins to absorb and fused silica or
quartz must be substituted.
• Also, in the IR region, glass, quartz, and fused silica
all absorb at wavelengths longer than about 2500nm.
• Hence, optical elements for IR spectrometry are
typically made from halide salts or In some cases
polymeric materials.

E.T 82
 Spectroscopic Sources
• To be suitable for spectroscopic studies,
– a source must generate a beam of radiation that is sufficiently powerful
to allow easy detection and measurement.
– its output power should be stable for reasonable periods of time.
• Typically, for good stability. a well-regulated power supply
must provide electrical power for the source.
• Spectroscopic sources are of two types:
• continuum sources, which emit radiation that changes in
intensity only slowly as a function of wavelength, and
• line sources, which emit a limited number of spectral lines,
each of which spans a very limited wavelength range.
• The distinction between these sources is illustrated in Figure 3.

E.T 83
 Fig. 3

E.T 84
• Continuous Sources of Ultraviolet -Visible, and Near-Infrared Radiation
• Tungsten Filament Lamps
• The most common source of visible and near-infrared radiation is the
tungsten filament lamp.
– The energy distribution of this source approximates that of a black body
and is thus temperature dependent.
• Figure below illustrates the behaviour of the tungsten filament lamp at
3000oK.In most absorption instruments, the operating filament
temperature is about 2900oK; the bulk of the energy is thus emitted in
the infrared region.

Figure 4 (a) A tungsten lamp of the type used in spectroscopy and its spectmm
(b). Intensity of the tungsten source is usually quite low at wavelengths shorter than about 350 nm.
Note that the intensity reaches a maximum in the near-IR region of the spectrum ( -1200 nm in this case).
E.T 85
• A tungsten filament lamp is useful for the
wavelength region between 320 and 2500 nm.
• In the visible region the energy output of a
tungsten lamp varies.
– As a consequence close voltage control is required
for a stable radiation source.
• Constant voltage transformers or electronic
voltage regulators are often employed for this
purpose

E.T 86
Hydrogen or Deuterium Lamps
• A truly continuous spectrum in the ultraviolet region is conveniently
produced by the electrical excitation of hydrogen or deuterium
at low pressure.
• The mechanism by which a continuum is produced involves the
formation of excited molecule (D2*or H2*) by absorption of
electrical energy.
• The species then dissociates to give two hydrogen or deuterium
plus ultraviolet photon.

H2 + Ee H2* H’ + H’’ + hʋ
The energy of the overall process is
Ee = E H2* = EH’ + EH’’ + hʋ
E H2* is fixed quantized energy of H2* , EH’ and EH’’
kinetic energy of H’ and H’’
E.T 87
• Most modern lamps for generating ultraviolet radiation
contain deuterium and are of a low-voltage lamps.
– an arc is formed between a heated, oxide-coated filament and a
metal electrode.
• The heated filament provides 'electrons to maintain a dc
current when a voltage of about 40 V is applied; a regulated
power supply is required for constant intensities.
• Both hydrogen and deuterium lamps produce a continuous
spectrum in the region of 160 to 375 nm.
• Quartz windows must be employed in the tubes, since glass
absorbs strongly in this wavelength region.
• Xenon Arc Lamps.
• This lamp produces intense radiation by the passage of
current through an atmosphere of xenon.
• The spectrum is continuous over the range between about
250 and 600 nm.

E.T 88
• Continuous Sources of Infrared radiation 
• The common infrared source is an inert solid heated
electrically to temperatures between
– 1500 and 2000oK.
• The Nernst glower is composed of Zirconium and
yttrium oxides formed into a cylinder having a diameter
of 2 mm and length of perhaps 20 mm,
• It emits infrared radiation when heated to a high
temperature by an electric current.
• The Globar Source
• A Globar is a silicon carbide rod, usually about 50 mm
in length and 5 mm in diameter.
• Radiation in the region 1 to 40 µm is emitted when the
Globar heated to 15000C by passage of electricity

E.T 89
• Line Sources
• Sources that emit a few discrete lines find use in atomic absorption spectroscopy,
Raman spectroscopy, refractometry, and polarimetry. 
• Hollow Cathode Lamps
• The most common source for atomic absorption
• which consists of a tungsten anode and a cylindrical cathode sealed in a glass tube
that is filled with neon or argon at a pressure of 1 to 5 torr
• The cathode is constructed of the metal whose spectrum is desired or serves As a
support for a coating of that metal.

E.T 90
 CELLS

UV Spectrophotometer
Quartz (crystalline silica)

 Visible Spectrophotometer
Glass

 IR Spectrophotometer
NaCl

E.T 91
Figure Typical examples of commercially available cells for the
UV/visible region. E.T 92
• Wavelength Selection
• Spectroscopic instruments generally required a device that
restricts the wavelength that is to be used to narrow band that
is absorbed or emitted by the analyte.
– Such device enhance selectivity and sensitivity of an instrument
• For absorption measurement, narrow bandwidths increase the
likelihood of adherence to Beer’s law.
• For this reason we usually try to select a single wavelength
where the analyte is the only absorbing species.
– Unfortunately, we cannot isolate a single wavelength of radiation from
a continuum source.
• Instead, a wavelength selector passes a narrow band of
radiation characterized by
– a nominal wavelength, an effective bandwidth, and a maximum
throughput of radiation.

E.T 93
• The effective bandwidth is defined as the width of the radiation at
half the maximum throughput.
• The ideal wavelength selector has a high throughput of radiation
and a narrow effective bandwidth.
– A high throughput is desirable because more photons pass through the
wavelength selector, giving a stronger signal with less background noise.
• A narrow effective bandwidth provides a higher resolution, with
spectral features separated by more than twice the effective
bandwidth being resolved.
E.T 94
• Generally these two features of a wavelength
selector are in opposition
• Conditions favouring a higher throughput of
radiation usually provide less resolution.
• Decreasing the effective bandwidth improves
resolution, but at the cost of a noisier signal.
• For a qualitative analysis, resolution is
generally more important than the throughput of
radiation; thus,
– smaller effective bandwidths are desirable.
• In a quantitative analysis a higher throughput of
radiation is usually desirable 
E.T 95
• Wavelength Selection Using Filters
• The simplest method for isolating a narrow band of radiation is
to use an absorption or interference filter.
• Absorption filters
• work by selectively absorbing radiation from a narrow region
of the electromagnetic spectrum .
– Limited application to visible region.
• A simple example of an absorption filter usually consist of a
colored glass plate that removes part of incident radiation by
absorption.
– A purple filter, for example, removes the complementary color green
from 500–560 nm.
– Commercially available absorption filters provide effective bandwidths
from 30–250 nm.
• Interference filters are more expensive than absorption filters,
but have narrower effective bandwidths, typically 10–20 nm,
with maximum throughputs ofE.Tat least 40%. 96
E.T 97
• Wavelength Selection Using Monochromators
• One limitation of an absorption or interference filter is that
they do not allow for a continuous selection of wavelength.
• If measurements need to be made at two wavelengths, then the
filter must be changed in between measurements.
• A further limitation is that filters are available for only
selected nominal ranges of wavelengths.
• An alternative approach to wavelength selection, which
provides for a continuous variation of wavelength, is the
– monochromator
• Monochromators for ultraviolet, visible, and infrared radiation
are all similar in mechanical construction in the sense that they
employ slits, lenses, mirrors, windows, and prisms or gratings.

E.T 98
• Components of Monochromator
• All monochromators contain an entrance slit, a collimating lens
or mirror to produce a parallel beam of radiation, a prism or
grating as a dispersing element and a focusing element,
• which projects a series of rectangular images of the entrance slit
upon a plane surface (the focal plane).

Infrared
monochromatic
Ray

Red
Orange
Yellow SLIT
Polychromatic Green
PRISM
Ray Blue
Violet

Ultraviolet

Polychromatic Ray Monochromatic Ray

E.T 99
Figure Types of monochromators: (a) grating monochromator: (b) prism
monochromator.
The monochromator design in (a) is a Czerny- Turner design. while the prism
monochromator in (b) is a Bunsen design. In both cases, , λ1 >λ2
E.T 100
• A source of radiation containing two wavelengths, λ1 and λ2, is
shown for purposes of illustration.
• This radiation enters the monochromators via a narrow
rectangular opening or slit, is collimated, and then strikes the
surface of the dispersing element at an angle.
• In the prism monochromator, refraction at the two faces results
in angular dispersal of the radiation, as shown;
• for the grating, angular dispersion results from diffraction,
which occurs at the reflective surface.
• In both designs, the dispersed radiation is focused on the focal
plane AB where it appears as two "images of the entrance slit
(one for each wavelength).

E.T 101
• Radiation detectors and Transducers 
• A detector is a device that indicates the existence of some
physical phenomenon.
• Photographic film indicating presence of EMR ,pointer of
balance indicating mass d/n, mercury level in thermometer
indicating temperature change.
– Early instruments for the measurement of emission and absorption of
radiation required visual or photographic methods for detection.
• A transducer is a special type of detector that converts signals,
such as light intensity, pH, mass and temperature into
electrical signals that can be subsequently amplified,
• manipulated and finally converted into numbers that are
related to the magnitude of the original signal.

E.T 102
• Properties of Transducers
• To be useful the detector must respond rapidly to low levels
of radiant energy over a broad wavelength range.
• produce an electrical signal that can be readily amplified, and
have a relatively low noise level (for stability).
• Finally, it is essential that the signal produced be directly
proportional to the beam power P; that is,
G = KP + K'
– where G is the electrical response of the detector in units of current.
resistance, or potential. The constant K measures the sensitivity of the
detector in terms of electrical response per unit of radiant power.
– Many detectors exhibit a small constant response known as a dark
currenl K'. even when no radiation impinges on their surfaces.

E.T 103
Types of Transducers
As indicated in Table,10.4 two general types of radiation transducers
are employed; one responds to photons, the other to heat.

E.T 104
• All photon detectors are based upon interaction of
radiation with a reactive surface to produce electrons
(photoemission) or
• to promote electrons to energy states in which they
can conduct electricity (photoconduction).
• Only ultraviolet, visible, and near-infrared radiations
have sufficient energy to cause these processes to
occur.
• Photoelectric detectors also differ from heat detectors
in that their electrical signal results from a series of
individual events (absorption of one photon).

E.T 105
• Photon Detectors
• Several types of photon detectors are available. including:
– photovoltaic cells, phototubes, photomultiplier tubes, semiconductor
detectors, silicon diodes and charge –transfer device
• Phototubes
• which consists of a semi cylindrical cathode and a wire
anode sealed inside an evacuated transparent envelope.
• The concave surface of the electrode supports a layer of
photoemissive material that tends to emit electrons upon
being irradiated.
• When a potential is applied across the electrodes, the
emitted electrons flow to the wire anode, generating a
photocurrent.
• The currents produced are generally about one-tenth as great as
those from a photovoltaic cell for
E.T
a given radiant intensity. 106
Figure A phototube and accompanying circuit. The photocurrent induced by
the radiation causes a voltage across the measuring resistor:
this voltage is then amplified and measured.

E.T 107
• The number of electrons ejected from a
photoemissive surface is directly proportional
to the radiant power of the beam striking that
surface.
• As the potential applied across the two
electrodes of the tube is about 90 V, the
fraction of the emitted electrons reaching the
anode to give current that is proportional to the
radiant power.
• Assignment Discuss in detail for the remaining
four type of detectors
E.T 108
• Heat detector
• Infrared radiation generally does not have sufficient energy to
produce a measurable current when using a photon transducer.
– A heat detector, therefore, is used for infrared spectroscopy.
• The absorption of infrared photons by a heat detector increases its
temperature, changing one or more of its characteristic properties.
• The pneumatic transducer, for example consists of a small tube
filled with xenon gas equipped with an IR-transparent window at
one end, and a flexible membrane at the other end.
• A blackened surface in the tube absorbs photons, increasing the
temperature and, therefore, the pressure of the gas.
• The greater pressure in the tube causes the flexible membrane to
move in and out, and this displacement is monitored to produce
an electrical signal.
 

E.T 109
• SIGNAL PROCESSORS AND READOUTS
• The signal processor is ordinarily an electronic
device that amplifies the electrical signal from
the detector; in addition, it may alter the signal
from dc to ac (or the reverse)
– change the phase of the signal, and filter it to remove
unwanted components.
• Furthermore, the signal processor may be called
upon to perform such mathematical operations
on the signal as differentiation integration, or
conversion to a logarithm.

E.T 110
 Chapter Four

Atomic Absorption and Emission

Spectroscopy

E.T 111
 ATOMIC SPECTROSCOPY

• Elemental analysis at the trace or ultratrace level can be

performed by a number of analytical techniques;
however, atomic spectroscopy remains the most
popular approach.
• Atomic spectroscopy can be subdivided into three
fields:
• Atomic emission spectroscopy (AES),
• Atomic absorption spectroscopy (AAS), and
• Atomic fluorescence spectroscopy (AFS)
• that differ by the mode of excitation and the method of
measurement of the atom concentrations.

E.T 112
• The selection of the atomic spectroscopic technique to
be used for a particular application should be based on
the desired result, since each technique involves
different measurement approaches.
• AES excites ground-state atoms and then quantifies the
concentrations of excited-state atoms by monitoring
their special deactivation.
• AAS measures the concentrations of ground-state
atoms by quantifying the absorption of spectral
radiation that corresponds to allowed transitions from
the ground to excited states.
• AFS determines the concentrations of ground-state
atoms by quantifying the radiative deactivation of
atoms that have been excited by the absorption of
discrete spectral radiation.

E.T 113
E.T 114
 Flame Atomic Emission
Spectroscopy
• Introduction Flame photometry, now more properly called
flame atomic emission spectrometry, is a relatively old
instrumental analysis method.
• Atomic emission is a fast, simple, and sensitive method for
the determination of trace metal ions in solution.
• Because of the very narrow (ca. 0.01 nm) and characteristic
emission lines from the gas-phase atoms in the flame
plasma, the method is relatively free of interferences from
other elements.
• The method is suitable for many metallic elements,
especially for those metals that are easily excited to higher
energy levels at the relatively cool temperatures of typical
flames – Na, K, Ca, Rb, Cs, Cu, and Ba.

E.T 115
 Theory
• Sample solution sprayed or aspirated as fine mist into flame.
• Conversion of sample solution into an aerosol by atomizer
(scent spray) principle.
– in this stage no chemical change in the sample
• Heat of the flame vaporizes sample constituents
– Solvent vaporizes leaves solid partial of salt
• By heat of the flame + action of the reducing gas (fuel),
molecules & ions of the sample species are decomposed and
reduced to give ATOMS.
– eg Na+ + e- --> Na 
• Heat of the flame causes excitation of some atoms into higher
electronic states. 
• Excited atoms revert to ground state by emission of light
energy, of characteristic wavelength; measured by detector.

E.T 116
E.T 117
• Flame Emission -> it measures the radiation
emitted by the excited atoms that is related to
concentration.
•  Atomic Absorption -> it measures the radiation
absorbed by the unexcited atoms that are
determined.
• Atomic absorption depends only upon the number
of unexcited atoms, the absorption intensity is not
directly affected by the temperature of the flame.
• The flame emission intensity in contrast, being
dependent upon the number of excited atoms, is
greatly influenced by temperature variations.
E.T 118
 Instrumentation:
• Flame photometer consists of following
components:
• Pressure regulators and flow meters for fuel gases
• Flame source
• The atomizing device
• Wavelength selectors: May be a filter or
Monochromator
• Photosensitive detectors
• Read out unit.  

E.T 119
E.T 120
E.T 121
• Requirements of flame:
• It should have proper temperature
• Temp. should remain constant throughout
operation.
• There should not be any fluctuation during
burning.
• Function flame includes:
– To convert the constituent of the liquid sample in to
vapor state.
– To decompose the constituent into atoms or simple
molecules.
– To electronically excite a fraction of the resulting
atomic or molecular spectra.
E.T 122
• Transformation of sample into vapour
• With a pneumatic nebulizer operated by a compressed
gas, the solution is aspirated from the sample container
and nebulized into a mist or aerosol of fine droplets.
• By desolvation, i.e., evaporation of the solvent from the
droplets, this mist is converted into a dry aerosol which
is volatilized in the flame.
• The atomization, i.e., the conversion of volatilized
analyte into free atoms is performed by the flame or
other atomizer.

E.T 123
• Nebulizers used in flame photometer
• According to the source of energy used for
nebulization as, for example, Pneumatic or
ultrasonic nebulizers.
• According to the relative position of the
capillaries for the nebulizing gas and the
aspirated liquid, e.g., angular and concentric
nebulizers

E.T 124
E.T 125
• Burners
• Flames are produced by means of a burner to
which fuel and oxidant are supplied in the form of
gases.
• With the premix burner, fuel and oxidant are
thoroughly mixed inside the burner housing
before they leave the burner ports and enter the
primary combustion or inner zone of the flame.
• This type of burner usually produces an
approximately laminar flame, and is commonly
combined with a separate unit for nebulizing the
sample.
• The direct-injection burner combines the function
of nebulizer and burner.

E.T 126
E.T 127
E.T 128
• Thermal energy in flame atomization is provided by the
combustion of a fuel–oxidant mixture.
• Common fuels and oxidants and their normal temperature
ranges are listed in Table 28.2. Of these, the air–acetylene
and nitrous oxide-acetylene flames are used most
frequently.

E.T 129
• Flame temperature:
• The optimum flame temp. depends upon several
factors as excitation energy of the element,
sensitivity of the measurement, Presence of other
elements etc.
• The temp. of flame lies between 1000OC and
3000OC.
• Mixture of coal gas and air do not give very hot
flames, because of presence of nitrogen.
• The cyanogens gas produces excellent spectra but
it is toxic.
• Acetylene and hydrogen are most frequent choice

E.T 130
 Atomic Absorption Spectroscopy （ AAS ）
 
• Atomic absorption spectroscopy is a quantitative method of
 
analysis that is applicable to many metals and a few nonmetals.
• The technique was introduced in 1955 by Walsh in Australia
(A.Walsh, Spectrochim. Acta, 1955, 7, 108) 
• A much larger number of the gaseous metal atoms will
normally remain in the ground state. 
• These ground state atoms are capable of absorbing radiant
energy of their own specific resonance wavelength. 
• If light of the resonance wavelength is passed through a flame
containing the atoms in question, then part of the light will be
absorbed. 
• The extent of absorption will be proportional to the number of
ground state atoms present in the flame. 
E.T 131
E.T 132
E.T 133
Instrumentation

E.T 134
E.T 135
E.T 136
E.T 137
E.T 138
E.T 139
E.T 140
E.T 141
E.T 142
E.T 143
E.T 144
E.T 145
E.T 146
E.T 147
E.T 148
E.T 149
E.T 150
E.T 151
 Application of Flame photometer
• Determination of Na+, K+, Ca++,Mg++ in
biological fluids (Serum, plasma & Urine),
Analysis of Industrial waste for pollutants
Hardness of water
• Determination of Heavy metal at trace and
ulteratrace level

E.T 152
 Chapter Five

UV-Visible spectroscopy
E.T 153
E.T 154
 UV-Visible spectrum
• The part of the electromagnetic radiation
spectrum that you are most familiar with is
"visible light" but
• this is just a small portion of all the possible
types
– Violet :400 - 420 nm
– Indigo : 420 - 440 nm
– Blue : 440 - 490 nm
– Green : 490 - 570 nm
– Yellow : 570 - 585 nm
– Orange :585 - 620 nm
– Red :   620 - 780 nm
E.T 155
 Ultraviolet and visible spectroscopy
• It is used to measure the multiple bonds or atomic
conjugation within the molecule.
• The UV-Visible region is subdivided as below
– Vacuum UV: 100-200 nm
– Near UV: 200 to 400 nm
– Visible region: 400 to 750 nm
• Vacuum UV is so named because molecule of air
absorb radiation in these region.
• The radiation is assessable only in special vacuum
equipments. E.T 156
 Basics of UV Light Absorption
• Ultraviolet/visible spectroscopy involves the
absorption of ultraviolet/visible light by a
molecule
• causing the promotion of an electron from a
ground electronic state to an excited electronic
state
• Absorption of this relatively high-energy light
causes electronic excitation.
• The easily accessible part of this region
(wavelengths of 200 to 800 nm)
• absorption only if conjugated pi-electron systems
are present.
E.T 157
• The visible region of the spectrum comprises
photon energies of 36 to 72 kcal/mole, and
• the near ultraviolet region, out to 200 nm,
extends this energy range to 143 kcal/mole.
• Ultraviolet radiation having wavelengths less than
200 nm is difficult to handle, and is seldom used
as a routine tool for structural analysis
• The energies are sufficient to promote or excite a
molecular electron to a higher energy orbital.
• The absorption spectroscopy carried out in this
region is sometimes called "electronic
spectroscopy".  

E.T 158
• Electronic transitions
– d and f electrons
– Charge transfer reactions
• and n (non-bonding) electrons

E.T 159
Absorption Involving d and f Electrons

• Most transition-metal ions absorb in the

ultraviolet or visible region of the spectrum.
• For the lanthanide and actinide series, the
absorption process results from electronic
transitions of 4f and 5f electrons;
• for elements of the first and second transition-
metal series, the 3d and 4d electrons are
responsible for absorption.

E.T 160
E.T 161
 D transitions
• Partially occupied d orbitals
– Transitions from lower to higher energy levels
• Splitting of levels due to spatial distribution

similar

Axial direction

E.T 162
 D transitions
• Binding ligands on axis have greater effect
on axial orbitals

E.T 163
 D transitions
• ∆ value dependent upon ligand field
strength
– <Br-<Cl-<F-<OH-<C2O42-~H2O<SCN-
<NH3<en<NO2-<CN-
– ∆ increases with increasing field strength
• f-f
– 4f and 5f (lanthanides and actinides)
– Sharper transitions

E.T 164
 Actinide transitions
5
6+
Pu (835 nm)

4+
4 Pu (489 nm)

Normal
Absorbance

3 Heavy
Light

0
400 500 600 700 800
Wavelength (nm)

Figure 2: UV-vis spectra of organic phases for

13M HNO3 system
E.T 165
 Charge-transfer Transitions
• Electron donor and acceptor characteristics
– Absorption involves e- transitions from donor to
acceptor
• SCN to Fe(III)
– Product is Fe(II) and neutral SCN
– Metal is acceptor
• An exception is the 1,10--phenanthroline complex of iron(II) or
copper(I),
where the ligand is the acceptor and the metal ion is the donor.

E.T 166
• and n (non-bonding) electrons

E.T 167
Sigma and Pi orbitals

E.T 168
Electronic transactions involved

E.T 169
E.T 170
 Electronic spectroscopy
• Out of the six transitions outlined, only the two
lowest energy ones (left-most, colored blue) are
achieved by the energies available in the 200 to
800 nm spectrum.
• As a rule, energetically favored electron
promotion will be from the highest occupied
molecular orbital (HOMO) to the lowest
unoccupied molecular orbital (LUMO), and the
resulting species is called an excited state
E.T 171
 Types of Transitions
• There are several types of electronic transitions available to
a molecule including:
• σ to σ * (alkanes)
• σ to π * (carbonyl compounds)
• π to π * (alkenes, carbonyl compounds, alkynes, azo
compounds)
• n to σ * (oxygen, nitrogen, sulfur, and halogen
compounds)
• n to π * (carbonyl compounds)
 
E.T 172
 σ σ * Transitions
• An electron in a bonding σ orbital is excited to the
corresponding antibonding orbital.
• The energy required is large.
• For example, alkanes as methane (which has only
C-H bonds, and can only undergo σ σ *
transitions)
• shows an absorbance maximum at 125 nm.
• Absorption maxima due to σ σ * transitions are
not seen in typical UV-Visible spectra (200 - 700
nm).
• σ bonds are very strong and requires higher
energy of vacuum UV.
E.T 173
Ethane

 
max = 135 nm (a high energy transition)

Absorptions having max < 200 nm are difficult to observe because

everything (including quartz glass and air) absorbs in this spectral region.

E.T 174
 nσ * Transitions
• Saturated compounds containing atoms with lone pairs
(non-bonding electrons) are capable of n σ * as transitions.
• These transitions usually need less energy than σ σ *
transitions.
• They can be initiated by light whose wavelength is in the
range 150 - 250 nm.
• The number of organic functional groups with n σ * peaks
in the UV region is small.
• These transitions are involved in saturated compound with
one hetero atom with unshared pair of electron i.e. saturated
halides, ethers, aldehydes, ketones, amines etc.
• These transitions are sensitive to hydrogen bonding eg
alcohol and ethers which absorbs at wavelength shorter than
185 nm therefore used as a solvent in UV
E.T 175
 π π * Transitions
• For molecules that possess π bonding as in alkenes,
alkynes, aromatics, acyl compounds or nitriles,
• energy that is available can promote electrons from a π
Bonding molecular orbital to a π Antibonding
molecular orbital (π * ).
• This is called a π π * transition.
• The absorption peaks for these transitions fall in an
experimentally convenient region of the spectrum (200
- 700 nm).
• These transitions need an unsaturated group in the
molecule to provide the π electrons.
  E.T 176
  
C C  
hv
= hv
=hc/
 
 
 
Example: ethylene absorbs at longer wavelengths:


E.T 177
 n π * Transitions
• Lone pairs that exist on Oxygen atoms and Nitrogen
atoms may be promoted from their non-bonding
molecular orbital to a π antibonding molecular orbital
within the molecule.
• This is called an n π * transition and
• requires less energy (longer wavelength) compared to
a π π * transition within the same chromophore.
• These are available in compounds with unsaturated
centers. eg. Alkenes. They requires lowest energy as
compare to others
 
E.T 178
C O
 
 
n hv
n

 
 
n 

E.T 179
 Conjugated systems:

C C

LUMO

HOMO

Preferred transition is between Highest Occupied Molecular Orbital

(HOMO) and Lowest Unoccupied Molecular Orbital (LUMO).
Note: Additional conjugation (double bonds) lowers the HOMO-LUMO energy gap:
Example:
1,3 butadiene: max = 217 nm ; = 21,000
1,3,5-hexatriene max = 258 nm ; = 35,000

E.T 180
 Similar structures have similar UV spectra:

O
O

max = 238, 305 nm max = 240, 311 nm max = 173, 192 nm

E.T 181
Table: absorption characteristics of some common chromophores

182
E.T
Activity one:
Transitions n-> σ *, π -> π*, n->π* , σ -> σ*, σ ->π*
Choose possible transitions from the above list for each
chromophores.
R-OH n-> σ *
R-O-R n-> σ *
R-CH2-R σ -> σ*
R-C≡C-R π -> π*
R-C≡N n->π*, π -> π*
R-CHO π -> π*, n->π*
RCOOH n->π*

E.T 183
Instrumentation: :

E.T 184
Figure: Instrumental designs for UV-visible photometers or spectrophotometers. In (a), a single-beam
instrument is shown. Radiation from the filter or monochromator passes through either the reference cell
or the sample cell before striking the photodetector. In (b), a double-beam-in-space instrument is shown.
Here, radiation from the filter or monochromator is split into two beams that simultaneously pass through
the reference and sample cells before striking two matched photodetectors. In the double-beam-in-time
instrument (c), the beam is alternately sent through reference and sample cells before striking a single
photodetector. only a matter of milliseconds separate the beams as they pass through the two cells.
E.T 185
 Instrumentation:
• A beam of light from a visible and/or UV light source
is separated into its component wavelengths by a prism
or diffraction grating.
• Each monochromatic (single wavelength) beam in
turn is split into two equal intensity beams by a half-
mirrored device.
• One beam, the sample beam , passes through a small
transparent container (cuvette) containing a solution of
the compound being studied in a transparent solvent.
• The other beam, the reference , passes through an
identical cuvette containing only the solvent.

E.T 186
• The intensities of these light beams are then measured
by electronic detectors and compared.
• The intensity of the reference beam, which should
have suffered little or no light absorption, is defined
as I0.
• The intensity of the sample beam is defined as I.
• Over a short period of time, the spectrometer
automatically scans all the component wavelengths in
the manner described.
• The ultraviolet (UV) region scanned is normally from
200 to 400 nm, and the visible portion is from 400 to
800 nm.
E.T 187
 Solvent effect:
• Different compounds may have very different
absorption maxima and absorbances.
• Intensely absorbing compounds must be examined in
dilute solution, so that significant light energy is
received by the detector, and this requires the use of
completely transparent (non-absorbing) solvents.
• The most commonly used solvents are water,
ethanol, hexane and cyclohexane.
• Solvents having double or triple bonds, or heavy
atoms (e.g. S, Br & I) are generally avoided.

E.T 188
• Solvents must be transparent in the region to
be observed; the wavelength where a solvent
is no longer transparent is referred to as the
cutoff
Table: solvents for the UV and Visible regions

E.T 189
 • H-bonding further complicates the effect of vibrational and
rotational energy levels on electronic transitions, dipole-
dipole interacts less so
• The more non-polar the solvent, the better (this is not
always possible)

Figure: effect of solvent on the absorption

E.T
spectrum of acetaldehy 190
The Spectrum
1. The x-axis of the spectrum is in wavelength; 200-350 nm for UV,
200-700 for UV-VIS determinations

2. Due to the lack of any fine structure, spectra are rarely shown in their
raw form, rather, the peak maxima are simply reported as a numerical
list of “lambda max” values or λmax

NH2

λmax = 206 nm
O O 252
317
376

E.T 191
The Spectrum
1. The y-axis of the spectrum is in absorbance, A

2. From the spectrometers point of view, absorbance is the inverse of

transmittance: A = log10 (p0/p)

3. From an experimental point of view, three other considerations

must be made:
i. a longer path length, l through the sample will cause
more UV light to be absorbed – linear effect

ii. the greater the concentration, c of the sample, the more

UV light will be absorbed – linear effect

iii. some electronic transitions are more effective at the

absorption of photon than others – molar absorptivity, ε
this may vary by orders of magnitude…

E.T 192
192
4. These effects are combined into the Beer-Lambert Law: A = ε c l

i. for most UV spectrometers, l would remain constant (standard

cells are typically 1 cm in path length)

ii. concentration is typically varied depending on the strength of

absorption observed or expected – typically dilute – sub .001
M

iii. molar absorptivities vary by orders of magnitude:

• values of 104-106 are termed high intensity absorptions
• values of 103-104 are termed low intensity absorptions
• values of 0 to 103 are the absorptions of forbidden
transitions

A is unit less, so the units for ε are cm-1 · M-1

5. Since path length and concentration effects can be easily factored
out, absorbance simply becomes proportional to ε, and the y-axis is
expressed as e directly or as the logarithm of ε
E.T 193
The Spectrum

E.T 194
 Terminology Chromophore:
• Chromophore: A covalently unsaturated group
responsible for electronic absorption.
• Or Any group of atoms that absorbs light whether or not
a color is thereby produced. Eg C=C, C=O, NO2 etc
• A compound containing chromophore is called
chromogen.
• There are two types of chromophore
– Independent chromophore: single chromophore is sufficient to
import color to the compound eg. Azo group
– Dependent chromophore: When more then one chromophore
is required to produce color.
• Eg acetone having 1 kentone group is colorless where as diacetyl
having two kentone group isE.Tyellow 195
 Auxochrome:
• A saturated group with non bonding electron when
attached to chromophore alters both wavelengths as
well as intensity of absorption. Eg OH, NH2, NHR
etc.
OR
• A group which extends the conjugation of a
chromophore by sharing of nonbonding electrons.

E.T 196
 Substituent Effects
• General – Substituents may have any of four
effects on a chromophore
• Bathochromic shift (red shift) – a shift to
longer λ; lower energy
• Hypsochromic shift (blue shift) – shift to
shorter λ; higher energy
• Hyperchromic effect – an increase in intensity
• Hypochromic effect - a decrease in intensity 
E.T 197
 Hyperchromic
Bathochromic
 Hypsochromic Hypochromic

200 nm 700 nm
E.T
• Substituent Effects
1. Conjugation – most efficient means of bringing about a
bathochromic and hyperchromic shift of an unsaturated
chromophore:
max nm 
H2C
CH2 175 15,000

217 21,000

258 35,000

465 125,000
-carotene

O
n  * 280 12
  * 189 900
O n  * 280 27
  * 213 7,100
E.T 199
• Substituent Effects
2. Conjugation – Alkenes
Extending this effect out to longer conjugated systems the
energy gap becomes progressively smaller:

Energy Lower energy =

Longer wavelengths

ethylene
butadiene
hexatriene
octatetraene 200
E.T
 Activity 1
What type of shift observed in 1&2,3&5 and
4&6
• max ᵋmax
Hypsoc
1 .CH3-COH 293 nm 12 hromic
&
2. CH3-COCl 235 nm 53 Hyperc
hromic

3. n  * 280 12
Bathoc
4.   * 189 900
Hyperc hromic
3&5 4&6 &
hromic
5. n  * 280 27 Hyperc
6.   * 213 7,100 hromic

E.T 201
• We will find that the effect of substituent groups can be reliably
quantified from empirical observation of known conjugated
structures and applied to new systems
• This quantification is referred to as the Woodward-Fieser Rules
which we will apply to two specific chromophores:
1. Conjugated dienes
2. Aromatic systems
A. Dienes
1. General Features
For acyclic butadiene, two conformers are possible – s-cis and s-trans

s-trans s-cis
The s-cis conformer is at an overall higher potential energy than the s-trans;
therefore the HOMO electrons of the conjugated system have less of a jump to
the LUMO – lower energy, longer wavelength

E.T 202
A. Dienes
1. General Features
Two possible   * transitions can occur for butadiene and 2
 4*

 
175 nm –forb. 175 nm
 
217 nm 253 nm

s-trans s-cis


The 2  4* transition is not typically observed:

• The energy of this transition places it outside the region
typically observed – 175 nm

• For the more favorable s-trans conformation, this transition is

forbidden
The 2  3* transition is observed as an intense absorption

E.T 203
A. Dienes
1. General Features
The 2  3* transition is observed as an intense absorption ( =
20,000+) based at 217 nm within the observed region of the UV

While this band is insensitive to solvent (as would be expected) it is

subject to the bathochromic and hyperchromic effects of alkyl
substituents as well as further conjugation

Consider:

max = 217 253 220 227 227 256 263 nm

E.T 204
A. Dienes
2. Woodward-Fieser Rules - Dienes
The rules begin with a base value for max of the chromophore being
observed:

acyclic butadiene = 217 nm

The incremental contribution of substituents is added to this base value

from the group tables:

Group Increment
Extended conjugation +30
Each exo-cyclic C=C +5
Alkyl +5
-OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60
E.T 205
A. Dienes
2. Woodward-Fieser Rules - Dienes
For example:

Isoprene - acyclic butadiene = 217 nm

one alkyl subs. + 5 nm
222 nm
Experimental value 220 nm

Allylidenecyclohexane
- acyclic butadiene = 217 nm
one exocyclic C=C + 5 nm
2 alkyl subs. +10 nm
232 nm
Experimental value 237 nm

E.T 206
Calculate wavelengths for the following compounds by using Woodward-Fieser
Rules

- acyclic butadiene = 217 nm

one exocyclic C=C + 5 nm

4 alkyl subs. +20 nm

242 nm

- acyclic butadiene = 217 nm

3 alkyl subs. +15 nm

232 nm

E.T 207
A. Dienes
3. Woodward-Fieser Rules – Cyclic Dienes
There are two major types of cyclic dienes, with two different base values

Heteroannular (transoid): Homoannular (cisoid):

 = 5,000 – 15,000  = 12,000-28,000

base max = 214 base max = 253

The increment table is the same as for acyclic butadienes with a couple
additions:

Group Increment
Additional homoannular +39
Where both types of diene
are present, the one with
the longer  becomes the
base
E.T 208
A. Dienes
3. Woodward-Fieser Rules – Cyclic Dienes
For example:
1,2,3,7,8,8a-hexahydro-8a-methylnaphthalene
heteroannular diene = 214 nm

3 alkyl subs. (3 x 5) +15 nm

1 exo C=C + 5 nm
234 nm

Experimental value 235 nm

E.T 209
A. Dienes
3. Woodward-Fieser Rules – Cyclic Dienes

heteroannular diene = 214 nm

4 alkyl subs. (4 x 5) +20 nm

1 exo C=C + 5 nm
C OH
O 239 nm

homoannular diene = 253 nm

4 alkyl subs. (4 x 5) +20 nm

1 exo C=C + 5 nm
C OH
O 278 nm

E.T 210
A. Dienes
3. Woodward-Fieser Rules – Cyclic Dienes
Be careful with your assignments – three common errors:

R
This compound has three exocyclic
double bonds; the indicated bond is
exocyclic to two rings

This is not a heteroannular diene; you would

use the base value for an acyclic diene

Likewise, this is not a homooannular diene;

you would use the base value for an acyclic
diene

E.T 211
Calculate wavelengths for the following compounds by using Woodward-Fieser
Rules

heteroannular diene = 214 nm

Extended conjugation + 30 nm
4 alkyl subs. (4 x 5) +20 nm
1 exo C=C + 5 nm
C OH
O
269 nm

homoannular diene = 253 nm

2 Extended conjugation + 60 nm
5 alkyl subs. (5 x 5) +25 nm
OCOCH3 -OCOH3 +0
2 exo C=C + 10 nm

348 nm

E.T 212
Practical application of UV spectroscopy
1. UV was the first organic spectral method, however, it is rarely
used as a primary method for structure determination

2. It is most useful in combination with NMR and IR data to

elucidate unique electronic features that may be ambiguous in
those methods

3. It can be used to assay (via max and molar absorptivity) the

proper irradiation wavelengths for photochemical experiments,
or the design of UV resistant paints and coatings

4. The most ubiquitous use of UV is as a detection device for

HPLC; since UV is utilized for solution phase samples vs. a
reference solvent this is easily incorporated into LC design

UV is to HPLC what mass spectrometry (MS) will be to GC

E.T 213
• Visible Spectroscopy
A. Color
1. General
• The portion of the EM spectrum from 400-800 is observable to
humans- we (and some other mammals) have the adaptation of
seeing color at the expense of greater detail

400 500 600 700 800

, nm
Violet 400-420
Indigo 420-440
Blue 440-490
Green 490-570
Yellow 570-585
Orange 585-620
Red 620-780
E.T 214
Visible Spectroscopy
Color
1. General
• When white (continuum of ) light passes through, or is reflected
by a surface, those that are absorbed are removed from the
transmitted or reflected light respectively

• What is “seen” is the complimentary colors (those that are not

absorbed)

• This is the origin of the “color wheel”

E.T 215
Visible Spectroscopy

• Organic compounds that are “colored” are typically those with

extensively conjugated systems (typically more than five)

• Consider -carotene

-carotene, max = 455 nm

max is at 455 – in the far blue region of the

spectrum – this is absorbed

The remaining light has the complementary

color of orange

E.T 216
Visible Spectroscopy
• Likewise:

lycopene, max = 474 nm

O
H
N

N
H
O
indigo

max for lycopene is at 474 – in the near blue region of the

spectrum – this is absorbed, the compliment is now red

max for indigo is at 602 – in the orange region of the

spectrum – this is absorbed, the compliment is now indigo!

E.T 217
• One of the most common class of colored organic molecules are the azo dyes:

N N

EWGs EDGs
• These materials are some of the more familiar colors of
our “environment”

NO2
HO

O3 S N N
H2N N N
N
N
NH2
OH
SO3

Fast Brown Sunset Yellow (Food Yellow 3)

Para Red

E.T 218
 • In the chemical sciences these are the acid-base indicators used for
the various pH ranges:

Methyl Orange

CH3 CH3
H
O3 S N N N O3 S N N N
CH3 CH3

Yellow, pH > 4.4 Red, pH < 3.2

E.T 219
 Quantitative applications of
UV/Vis spectroscopy
• quantitative analysis of samples
• environmental chemistry
– for the analysis of waters and wastewaters
• clinical chemistry
– analysis of different analytes such as total serum protein,
serum cholesterol, uric acid, glucose, protein-bound iodine
• industrial chemistry
– for the analysis of a diverse array of industrial samples, including
pharmaceuticals, food, paint, glass, and metals.
• forensic chemistry
– blood alcohol using the Breathalyzer test

E.T 220
 Chapter 6
Infrared Spectroscopy

E.T 221
 determine the chemical functional groups in the
sample.
• Different functional groups absorb characteristic
frequencies of IR radiation.
• Using various sampling accessories, IR
spectrometers
can accept a wide range of sample types such as
gases,
liquids, and solids. Thus,
• IR spectroscopy is an important and popular tool
for
structural elucidation and compound identification
• Infrared radiation takes a section of the
electromagnetic
spectrum having wavenumbers from roughly
13,000 to 10 cm–1, or wavelengths
E.T from 0.78 to 222
wavenumbers are directly proportional to frequency, as well as
the energy of the IR absorption

E.T 223
Principle: chemical bonds rotate or vibrate at specific
frequencies
• Most electronic transitions require energies in the
uv or
vis regions;
• Absorption of infrared radiation is thus confined
largely
to molecular species for which small energy
differences
exist between various vibrational and rotational
states.
 In order to absorb infrared radiation, a molecule
must
undergo a net change in dipole moment as a
consequence of its vibrational or rotational
motion E.T 224
magnitude of
the charge difference and the distance between
the two
centers of charge.
 As a hydrogen chloride molecule vibrates
longitudinally, a regular fluctuation in dipole
moment
occurs, and a field is established which can
interact
with the electrical field associated with radiation.
 If the frequency of the radiation matches a natural
vibrational frequency of the molecule, there occurs
a net
transfer of energy that results in a change in the
amplitude of the molecular vibration:
 absorption of the radiation
E.T
is the 225
• No net change in dipole moment occurs during the
vibration or rotation of homonuclear species such
as O2 , N2, or Cl2;
 consequently such compounds cannot absorb in
the infrared

E.T 226
 Molecular Vibrations.
The approximation is ordinarily made that the behaviour of
a
molecular vibration is analogous to the mechanical model.
Thus,
the frequency of the molecular vibration is calculated from

• The masses of the two atoms for m1 and m2;" the quantity k
becomes the force constant for: the chemical bond,
• which is a measure of its: stiffness (but not necessarily its
strength). E.T 227
coordinate
axes (x, y, z).
 A polyatomic molecule of n atoms has 3n total
degrees
of freedom.
 However, 3 degrees of freedom are required to
describe
translation, the motion of the entire molecule
through
space.
 Additionally, 3 degrees of freedom correspond to
rotation of the entire molecule.
• Therefore, the remaining 3n – 6 degrees of
freedom are
true, fundamental vibrations for nonlinear
molecules. E.T 228
 Among the 3n – 6 or 3n – 5 fundamental vibrations (also
known as normal modes of vibration),
 those that produce a net change in the dipole moment
may
result in an IR activity
• The total number of observed absorption bands is
generally
different from the total number of fundamental vibrations.
 It is reduced because some modes are not IR active and
a single frequency can cause more than one mode of
motion to occur.
• Conversely, additional bands are generated by the
appearance of overtones (integral multiples of the
fundamental absorption frequencies),
• combinations of fundamental frequencies, differences of
fundamental frequencies, coupling interactions of two
fundamental absorption frequencies, and coupling
interactions between fundamental
E.T
vibrations and overtones229
or combination bands (Fermi resonance).
• The intensities of overtone, combination, and difference bands
are
less than those of the fundamental bands.
• The combination and blending of all the factors thus create a
unique IR spectrum for each compound.
• The major types of molecular vibrations are stretching and
bending.
• The various types of vibrations are illustrated in Fig. below
• Infrared radiation is absorbed and the associated energy is
converted
into these type of motions.
•The absorption involves discrete, quantized energy levels.
• However, the individual vibrational motion is usually
accompanied
by other rotational motions.
• These combinations lead to the absorption bands, not the
discrete
lines, commonly observed in the mid IR region.
E.T 230
Figure: Types of molecular vibrations. note that + indicates motion from the page
toward the reader and - indicates motion away from the reader.

E.T 231
Instrumentation
There are 3 types of IRs.
• Dispersive, FTIRs (Fourier Transform Infrared
Spectrophotometer) and Filter photometers
• Dispersive uses heated solid source and changes frequency
over
time by moving grating, mirror or detector. Originally used
prisms and later grating.
Detectors respond for heat than photon
• Largely replaced by Fourier Transform – Allows for all
frequencies to be measured at once:
A FTIR Uses a Moving Mirror and Powerful Computer
Calculations to Determine Which Wavelengths of IR Energy
Were Absorbed
advantage – No slits: Better speed and sensitivity
• Filter photometers :Designed to monitor the concentration of
air pollutantes such as CO
E.T 232
A Dispersive IR Spectrophotometer

Figure: Schematic diagram of a double-beam, dispersive IR spectrophotometer. The

heavy black lines indicate mechanical linkages, and the light lines indicate electrical
connections. The radiation path is designated by dashed lines.
E.T 233
IR Spectrum
Plot IR energy vs. %transmittance (%T)
– Energy scale in wave numbers, wn (cm-1)
– %T scale
• Compares intensity of IR striking sample (Iin) with intensity of
IR leaving sample (Iout)
• 100%T no light absorbed by sample
• 0% all light absorbed by sample

E.T 234
Record
– Wave number location of IR “band” (position of max %T)
– Intensity of IR “band”
s = strong (low %T), m = medium, w = weak (high %T)
vs = very strong, vw = very weak

E.T 235
E.T 236
Characteristic Absorptions

E.T 237
E.T 238
IR Major Regions to Examine

E.T 239
E.T 240
IR spectra of ALKANES
C—H bond “saturated”
(sp3) 2850-2960 cm-1
+ 1350-1470 cm-1
-CH2- bend + 1430-1470
-CH3 bend + “ and 1375
-CH(CH3)2 + “ and 1370, 1385
-C(CH3)3 + “ and 1370(s), 1395 (m)

E.T 241
 n-pentane

2850-2960
3000 cm-1 cm-1
sat’d C-H
1470 &1375 cm-1

CH3CH2CH2CH2CH3
E.T 242
n-hexane

CH3CH2CH2CH2CH2CH3
E.T 243
2-methylbutane
(isopentane)

E.T 244
2,3-dimethylbutane

E.T 245
cyclohexane

no 1375 cm-1
no –CH3

E.T 246
IR of ALKENES
=C—H bond, “unsaturated” vinyl
(sp2) 3020-3080 cm-1
bend + 675-1000
RCH=CH2 + 910-920 & 990-1000
R2C=CH2 + 880-900
cis-RCH=CHR + 675-730 (v)
trans-RCH=CHR + 965-975

C=C bond 1640-1680 cm-1 (v)

E.T 247
 1-decene

unsat’d
C-H

3020-
3080
cm-1 910-920 &
990-1000
C=C 1640-1680 RCH=CH2

E.T 248
4-methyl-1-pentene

910-920 &
990-1000
RCH=CH2

E.T 249
2-methyl-1-butene

880-900
R2C=CH2

E.T 250
2,3-dimethyl-1-butene

880-900
R2C=CH2

E.T 251
IR spectra BENZENEs
=C—H bond, “unsaturated” “aryl”
(sp2) 3000-3100 cm-1
+ 690-840
mono-substituted + 690-710, 730-770
ortho-disubstituted + 735-770
meta-disubstituted + 690-710, 750-810(m)
para-disubstituted + 810-840(m)

C=C bond pairs 1500, 1600 cm-1

E.T 252
 ethylbenzene

3000-
3100
cm-1
Unsat’
1500 & 1600
d C-H 690-710,
Benzene ring
730-770
mono-

E.T 253
o-xylene

735-
770
ortho

E.T 254
p-xylene

810-840(m)
para

E.T 255
m-xylene

meta

690-710,
750-
810(m)

E.T 256
styrene

no sat’d C-H

1640
C=C 910-920 &
990-1000
RCH=CH2 mono

E.T 257
IR spectra ALCOHOLS & ETHERS

C—O bond 1050-1275 (b) cm-1

1o ROH 1050
2o ROH 1100
3o ROH 1150
ethers 1060-1150

O—H bond (broad peak) 3200-3640 (b) 

E.T 258
 1-butanol

3200-3640 (b) O-
H

C-O 1o

CH3CH2CH2CH2-OH
E.T 259
 2-butanol

O-H
C-O 2o

E.T 260
 tert-butyl alcohol

O-H
C-O 3o

E.T 261
 methyl n-propyl ether

no O--H

C-O ether

E.T 262
2-butanone

 C=O
~1700 (s)

E.T 263
 C9H12

1500 & 1600

benzene

C-H unsat’d & sat’d mono

C9H12 – C6H5 = -C3H7

isopropylbenzene
n-
E.T propylbenzene? 264
n-propylbenzene

E.T 265
isopropylbenzene

isopropyl split 1370 + 1385

E.T 266
 C8H6

C-H 1500, 1600

unsat’d benzene

3300 C8H6 – C6H5 = C2H

C-H mono

phenylacetylene

E.T 267
C4H8

Unst’d

1640- 880-
1680
900
C=C
R2C=CH2

isobutylene CH3
CH3C=CH2

E.T 268
Which compound is this?
a) 2-pentanone 1-pentanol
b) 1-pentanol
c) 1-bromopentane
d) 2-methylpentane E.T 269
What is the compound?
a) 1-bromopentane 2-pentanone
b) 1-pentanol
c) 2-pentanone
d) 2-methylpentane E.T 270
In a “matching” problem, do not try to fully analyze each spectrum. Look for
differences in the possible compounds that will show up in an infrared
spectrum.

H2 H2 H2
A C C C CH2 E C C
H

biphenyl allylbenzene 1,2-diphenylethane

CH3
CH3
D CH3CH2CH2CH2CH3 F CH2CH2CH2CH3
B

o-xylene n-pentane n-butylbenzene

E.T 271
1

E.T 272
2

E.T 273
3

E.T 274
4

E.T 275
5

E.T 276
6

E.T 277
 Chapter 7
NMR Spectroscopy

Ephrem T. 278
• A strong magnetic field causes the energies of certain nuclei
to be split into two or more quantized levels, owing to the
magnetic properties of these particles.
• Transitions among the resulting magnetically 'induced energy
levels can be brought about by the absorption of EMR of
suitable frequency,
• just as electronic transitions are caused by the absorption of
ultraviolet or visible radiation.
• The energy differences between magnetic quantum levels for
atomic nuclei correspond to radiation energies in the
frequency range of O.l to l00MHz (wavelengths between 3000
and 3 m),
• which is in the radio-frequency portion of the
electromagnetic spectrum.

Ephrem T. 279
The nuclei of many isotopes have a characteristic spin (I).
• Integral spins (e.g. I = 1, 2, 3 ....),
• Fractional spins (e.g. I = 1/2, 3/2, 5/2 ....),
• No spin, I = 0 (e.g. 12C, 16O, 32S, ....).
• Isotopes of particular interest and use to organic
chemists are
• 1H, 13C, 19F and 31P, all of which have I = 1/2.
Spin Properties of Nuclei
• Nuclear spin is related to the nucleon composition:
• Odd mass nuclei (i.e. those having an odd number of
nucleons) have fractional spins.
Examples: I = 1/2 ( 1H, 13C, 19F )

Ephrem T. 280
I = 3/2 ( 11B )
I = 5/2 ( 17O )
• Even mass nuclei composed of odd numbers of protons
and neutrons have integral spins.
• Examples: I = 1 ( 2H, 14N )
• Even mass nuclei composed of even numbers of protons
and neutrons have zero spin ( I = 0 ).
• Examples: 12C and 16O
• Spin 1/2 nuclei have a spherical charge distribution, and
their NMR behavior is the easiest to understand.
• All nuclei with non-zero spins have magnetic moments
(μ).

Ephrem T. 281
Ephrem T. 282
Ephrem T. 283
Ephrem T. 284
Ephrem T. 285
Ephrem T. 286
Ephrem T. 287
Ephrem T. 288
Ephrem T. 289
Ephrem T. 290
Ephrem T. 291
Ephrem T. 292
Ephrem T. 293
CL Activity 1: nuclear spin states
1.List allowed spin state with spin quantum number
2 & 5/2.

m= I,I-1,I-2,……. –I
eq. 2I+1
2x2+1= 5 2, 1,0,-1,-2
2x5/2+1= 6 5/2,3/2, ½,-1/2, -3/2, -5/2

Ephrem T. 294
 Magnetic Shielding
• If all protons absorbed the same amount of
energy in a given magnetic field, not much
information could be obtained.
• But protons are surrounded by electrons
that shield them from the external field.
• Circulating electrons create an induced
magnetic field that opposes the external
magnetic field. =>

Ephrem T. 295
 Shielded Protons
Magnetic field strength must be increased for
a shielded proton to flip at the same
frequency.

=>

Ephrem T. 296
 Protons in a Molecule
Depending on their chemical environment,
protons in a molecule are shielded by
different amounts.

=>
Ephrem T. 297
 NMR Signals
• The number of signals shows how many
different kinds of protons are present.
• The location of the signals shows how
shielded or deshielded the proton is.
• The intensity of the signal shows the number
of protons of that type.
• Signal splitting shows the number of protons
on adjacent atoms. =>
Ephrem T. 298
The NMR Spectrometer

=>
Ephrem T. 299
Ephrem T. 300
Ephrem T. 301
Ephrem T. 302
Resonance: the absorption of electromagnetic
radiation by a nucleus and the flip of its nuclear
spin from a lower energy state to a higher energy
state.
The instrument detects this and records it as
a signal

Ephrem T. 303
Ephrem T. 304
Why should the proton nuclei in different compounds
behave differently in the NMR experiment ?
Since electrons are charged particles, they move in response to
the external magnetic field (Bo) so as to generate a secondary
field that opposes the much stronger applied field.

Ephrem T. 305
The secondary field shields the nucleus from the applied field, so
Bo must be increased in order to achieve resonance (absorption of
RF energy.

Ephrem T. 306
Chemical Shift
The location of different NMR resonance signals is dependent on
both the external magnetic field strength and the RF frequency.

Ephrem T. 307
The location of an NMR signal in a spectrum is reported
relative to a reference signal from a standard compound
added to the sample.
A reference standard should be
1. Chemically unreactive
2. Easily removed from the sample after the measurement
3. Should give a single sharp NMR signal that does not
interfere with the resonances normally observed for
organic compounds.
Tetramethylsilane, (CH3)4Si, usually referred to as TMS,
meets all these characteristics

Ephrem T. 308
Ephrem T. 309
To correct these frequency differences for their field
dependence, these differences are divided by the spectrometer
frequency (100 or 500 MHz in the example)

Ephrem T. 310
This operation gives a locator number called the Chemical Shift,
having units of parts-per-million (ppm), and designated by the
symbol δ.

Ephrem T. 311
Commonly used solvents:
• CCl4 – no interfering H, but poor solvent for many polar
compounds and is also toxic.
• Deuterium labeled compounds: deuterium oxide
(D2O), chloroform-d (DCCl3), benzene-d6 (C6D6),
acetone-d6 (CD3COCD3) and DMSO-d6 (CD3SOCD3) are
now widely used as NMR solvents.
• Deuterium is invisible in a spectrometer tuned to protons.
• One factor contributing to chemical shift differences in
proton resonance is the inductive effect.
• The shielding effect in protons with high electron density
is large, and a higher external field (Bo) will be needed
for the RF energy to excite the nuclear spin.
Ephrem T. 312
Example
• Since Si is less EN than C, the electron density about the
methyl hydrogens in Si(CH3)4 is expected to be greater
than the electron density about the methyl hydrogens in
C(CH3)4.
• The protons in TMS (with high e density) are said be
shielded, and lie at higher magnetic field (upfield).
• Elements that are more electronegative than carbon
should exert an opposite effect (reduce the electron
density).
• Methyl groups bonded to such elements display lower
field (downfield) signals (they are deshielded).

Ephrem T. 313
Ephrem T. 314
Ephrem T. 315
Signal Strength
The magnitude of NMR signals is proportional to the
molar concentration of the sample.
Example
For equal molar amounts of benzene and cyclohexane,
the signal from cyclohexane will be twice as intense as
that from benzene because cyclohexane has twice as
many hydrogens per molecule.

•Similarly, for samples incorporating two or more

different sets of hydrogen atoms, the ratio of hydrogen
atoms in each distinct set can be determined.

Ephrem T. 316
Methods
1) Through horizontal integrator trace (light green) which
rises as it crosses each signal by a distance proportional to
the signal strength.

Ephrem T. 317
Ephrem T. 318
Ephrem T. 319
 =>

=>
Ephrem T. 320
Activity 1 Structurally Equivalent Atoms & Groups
For each of the compounds A through F indicate the number of structurally
distinct groups of equivalent hydrogens

Ephrem T. 321
Ephrem T. 322
Influence of Hydrogen Bonding
• The OH proton signal is seen at 2.37 δ in 2-methyl-3-butyne-2-ol,
and at 3.87 δ in 4-hydroxy-4-methyl-2-pentanone.
• A six-membered ring intramolecular hydrogen bond in the latter
compound is in part responsible for its low field shift.

Ephrem T. 323
π-Electron Functions
Anomalous observations from chemical shift chart:
1. The low field resonance of hydrogens bonded to
double bond or aromatic ring carbons.
2. the very low field signal from aldehyde hydrogens.
3. The hydrogen atom of a terminal alkyne, in contrast,
appears at a relatively higher field.
All these anomalous cases seem to involve hydrogens
bonded to pi-electron systems.
The field induced pi-electron movement produces strong
secondary fields that perturb nearby nuclei.
Example:
The pi-electrons associated with a benzene ring

Ephrem T. 324
The electron cloud above and below the plane of the ring
circulates in reaction to the external field so as to generate an
opposing field at the center of the ring and a supporting field
at the edge of the ring.

This kind of spatial variation is called anisotropy, and it is

common to nonspherical distributions of electrons

Ephrem T. 325
Regions in which the induced field supports or adds to the
external field are said to be deshielded.
• Regions in which the induced field opposes the external field are
termed shielded.
The anisotropy of some important unsaturated functions

Ephrem T. 326
 Spin-Spin Interactions
Consider the dichloroethane isomers.

1,2-dichloroethane 1,1-dichloroethane
displays a single the two signals from the
resonance signal from different hydrogens are split
the four structurally into close groupings of two or
equivalent hydrogens Ephrem T.
more resonances. 327
The signal splitting in proton spectra is usually small, ranging
from fractions of a Hz to as much as 18 Hz, and is designated as
J (referred to as the coupling constant).
In the 1,1-dichloroethane example all the coupling constants are
6.0 Hz.

Ephrem T. 328
Causes of signal splitting, and useful information
obtained from it.
If an atom under examination is influenced by a nearby
nuclear spin (or set of spins), the observed nucleus
responds to such influences.
• This spin-coupling is transmitted through the connecting
bonds, and it functions in both directions.
• For spin-coupling to be observed, the sets of interacting
nuclei must be bonded in relatively close proximity (e.g.
vicinal and geminal locations), or be oriented in certain
optimal and rigid configurations.

Ephrem T. 329
Some spectroscopists place a number before the symbol J to
designate the number of bonds linking the coupled nuclei
(colored orange below).

a vicinal coupling constant is 3J and a geminal constant is 2J.

General rules summarizing important requirements and

characteristics for spin 1/2 nuclei :
1.Nuclei having the same chemical shift (called isochronous) do

not exhibit spin-splitting.

Ephrem T. 330
2. Nuclei separated by three or fewer bonds (e.g. vicinal
and geminal nuclei ) will usually be spin-coupled and will
show mutual spin-splitting of the resonance signals (same
J's),
• provided they have different chemical shifts.
• Longer-range coupling may be observed in
molecules having rigid configurations of atoms.
3. The magnitude of the observed spin-splitting depends
on many factors and is given by the coupling constant J
(units of Hz).
• J is the same for both partners in a spin-splitting
interaction and is independent of the external magnetic
field strength.
4. The splitting pattern of a given nucleus (or set of
equivalent nuclei) can be predicted
Ephrem T.
by the n+1 rule. 331
n is the number of neighboring spin-coupled nuclei with the
same (or very similar) Js.
Example
If there are 2 neighboring, spin-coupled, nuclei the observed
signal is a triplet ( 2+1=3 ).

Ephrem T. 332
The intensity ratio of the lines is given by the numbers in
Pascal's triangle.

Thus, a doublet has 1:1 or equal intensities, a triplet has

an intensity ratio of 1:2:1, a quartet 1:3:3:1, etc.
Ephrem T. 333
If a given nucleus is spin-coupled to two or more sets of
neighboring nuclei by different J values, the splitting due to one
J set is added to that expected from the other J sets.

Ephrem T. 334
Splitting for Ethyl Groups

=>

Ephrem T. 335
Ephrem T. 336
Ephrem T. 337
Pairs of isomers (A & B) which display similar proton NMR
spectra

These difficulties would be largely resolved if the carbon atoms of a

molecule could be probed by NMR in the same fashion as the
hydrogen atoms.
Fortunately, 1.1% of elemental carbon is the 13C isotope, which has
a spin I = 1/2, so in principle it should be possible to conduct a
carbon NMR experiment.
It is worth noting, that if much higher abundances of 13C were
naturally present in all carbon compounds, proton NMR would
become much more complicated due to large one-bond coupling
of 13C and 1H. Ephrem T. 338
Obstacles needed to be overcome before carbon NMR
emerged as a routine tool:
i) As noted, the abundance of 13C in a sample is very low
(1.1%), so higher sample concentrations are needed.
ii) The 13C nucleus is over fifty times less sensitive than a
proton in the nmr experiment, adding to the previous
difficulty.
iii) Hydrogen atoms bonded to a 13C atom split its NMR
signal by 130 to 270 Hz, further complicating the NMR
spectrum.
Solution
Use of high-field pulse technology coupled with broad-
band heteronuclear decoupling of all protons.

Ephrem T. 339
Unlike proton NMR spectroscopy, the relative strength of
carbon NMR signals are not normally proportional to the
number of atoms generating each one.
13
C Chemical Shift Ranges

Ephrem T. 340
The isomeric pairs previously cited as giving very similar proton
NMR spectra are now seen to be distinguished by carbon NMR.

Ephrem T. 341
 Structurally Equivalent Atoms & Groups
For each of the compounds A through F indicate the number of
structurally distinct groups of carbon atoms, and also the number
of distinct groups of equivalent hydrogens.

Ephrem T. 342
Activity 2 Structurally Equivalent Atoms & Groups
For each of the compounds A through F indicate the number of structurally
distinct groups of equivalent carbons.

Ephrem T. 343
1. You have three unlabeled vials each containing a
trichlorobenzene isomer. In order to correctly identify each
compound and properly label its container you have taken their 13C
nmr spectra. Match the spectrum characteristics given below with a
compound from the following group:
1,2,3-trichlorobenzene
1,2,4-trichlorobenzene
1,3,5-trichlorobenzene

13
C NMR:
(i)Two peaks between δ125 and 140 ppm
1,3,5-trichlorobenzene
(ii) Six peaks between δ125 and 140 ppm
1,2,4-trichlorobenzene
(iii) Four peaks between δ125 and 140 ppm
1,2,3-trichlorobenzene
Ephrem T. 344
 Spin-Spin Splitting

• It is unlikely that a 13C would be adjacent to

another 13C, so splitting by carbon is
negligible.
• 13C will magnetically couple with attached
protons and adjacent protons.
• These complex splitting patterns are
difficult to interpret.

Ephrem T. 345
Proton Spin Decoupling

• To simplify the spectrum, protons are

continuously irradiated with “noise,” so
they are rapidly flipping.
• The carbon nuclei see an average of all the
possible proton spin states.
• Thus, each different kind of carbon gives a
single, unsplit peak.

Ephrem T. 346
Off-Resonance Decoupling

• C nuclei are split only by the protons

13

attached directly to them.

• The N + 1 rule applies: a carbon with N
number of protons gives a signal with
N + 1 peaks.

Ephrem T. 347
 Interpreting 13C NMR

• The number of different signals indicates the

number of different kinds of carbon.
• The location (chemical shift) indicates the
type of functional group.
• The peak area indicates the numbers of
carbons (if integrated).
• The splitting pattern of off-resonance
decoupled spectrum indicates the number of
protons attached to the carbon. =>
Ephrem T. 348
Two 13C NMR Spectra

=>
Ephrem T. 349
Using DEPT to Count the Hydrogens Attached to 13C
(Distortionless Enhancement of Polarization Transfer)

In DEPT, a second transmitter irradiates 1H during the

sequence, which affects the appearance of the 13C
spectrum.
some 13C signals stay the same
some 13C signals disappear
some 13C signals are inverted

Ephrem T. 350
Ephrem T. 351
Ephrem T. 352
 MRI
• Magnetic resonance imaging,
• “Nuclear” is omitted because of public’s fear
that it would be radioactive.
• Only protons in one plane can be in resonance
at one time.
• Computer puts together “slices” to get 3D.
• Tumors readily detected.

Ephrem T. 353
Spin-Spin Splitting in 1H NMR
What splitting pattern in the 1H nmr spectrum would you expect
for the hydrogen atom(s) colored red in the compounds shown
below?
Your choices are: s singlet d doublet t triplet q quartet
m multiplet

Ephrem T. 354
Mass Spectroscopy

CHAPTER 8
 Point of Mass Spectroscopy
• Determine a molecular mass for a sample.
• Use the molecular mass to determine possible
molecular formulas
• Determine pieces of the molecule from the
fragmentation pattern.
• Use this information to make a guess about the
structure or identity of the molecule.
• NOTE: This information alone is not enough to fully
characterize a molecule. Other spectral data would be
necessary.
356
 How Mass Spec Works
• A sample is injected
into a GC/MS.
• Components are
separated through GC.
• Each item goes through
a mass spectrometer
• A mass spectrum for
each compound is
detected and recorded

357
358
 The guts of it
• Already in the gas phase
molecules are bombarded by
high energy electrons.
• Knock an electron out of the
molecule generates the
Molecular ion (M+.)
• M+. fragments
• All charged species are
accelerated through a
magnetic field based on their
mass-to-charge ratio (m/z)

359
What comes out?
• A plot of m/z versus
relative abundance
• The tallest peak is
the base peak and
everything else is
relative to that
• The highest
numbered peak is
probably the
molecular ion
• All other peaks are
fragments

360
 Still not sure what that graphy thing
is?
• Only charged species are
deflected through the
magnetic field to the
detector
• Multiple masses are shown
• These masses are indicative
of how the molecular ion
split up
• Figuring out the pieces is
like doing a puzzle
• A puzzle for nerds

361
 The Mass Spectrum
Example: methane CH4 + e-  CH4+. + 2 e-
m/z = (1 x 12) + (4 x 1) = 16
C H
Base peak: most abundant ion
Relative ion abundance (%)

mass-to-charge ratio (m/z)

362
 The Mass Spectrum

Alternate data presentation...

m/z (amu) Relative abundance (%)
18 < 0.5 M+2 14
C1H4 or 12C3H1H3 or...
17 1.1 M+1 C H4 or 12C2H1H3
13 1

16 100.0 M C H4
12 1

15 85.0 M-H
16 9.2 M - 2H
17 3.0 M - 3H
12 1.0 M - 4H

Molecular ion (M): intact ion of substance being analyzed

Fragment ion: formed by cleavage of one or more bonds on molecular ions

363
 Lets Go!
Base peak = 43

 This is a hydrocarbon

 It has an even number for its

mass

 Assume that there are carbon

atoms

 Carbon has a mass of 12

 Hydrogen has a mass of 1

Molecular ion peak = 114

364
 Math it up
• Assume there is nothing • 9 carbon atoms has a
but Carbon and Hydrogen mass of 108
in it • 114 – 108 = 6
• Divide 114/12 = 9 • There could be 9 carbons
• There are up to 9 carbon and 6 hydrogens (C9H6)
atoms in the molecule • Not very likely
• If there were 8 carbons
then
– 114 – 96 = 18
– C8H18
• Probable

365
 Look for evidence
Fragmentation
• C8H18 is octane. This would
contain CH3 and CH2 groups.
– CH3 = 15
– CH3CH2 = 15+14=29
– CH3CH2CH2 = 15+14+14=43
• Do you see evidence of
these peaks?
• Commonly look for
m/z – base peak = ?

366
 Tips for doing this
• Know atomic and • Look at the difference
molecular masses between molecular ion
– Carbon =12 and base peak or other
– Hydrogen = 1 prominent peaks
– Nitrogen = 14, etc. • Subtract out non-carbon
• Look at the molecular ion atom masses and divide
peak. remainder by 12
– Odd # = odd number of – The integer refers to the
Nitrogen atoms (1, 3, etc.) maximum number of C’s
– Even # = zero or even – Remember that 12 H’s
number of Nitrogen atoms have the mass of 1 C
(0, 2, 4, etc.)

367
 Isotopes
• Rougly 1% of the C in the world is 13C.
• About 1/3 (~37%) of Chlorine is 37Cl. The rest is
35Cl.

– Makes M+2 peaks in a 3:1 ratio.

• About 50% of Bromine is 79Br. The rest is 81Br.
– Makes M+2 peaks in a 1:1 ratio.
• Look for M and M+2 peaks and try to determine
if these halogens have been (fragmentation) or
are present.

368
Isotopic Abundance

81
Br
=>

369
370
371
 Mass Spectrum  Formula  Structure
How do we derive structure from the mass spectrum?

CH3
?
 H C Cl

CH3

•Not trivial to do this directly

•Structure comes from formula; formula comes from mass spectrum

CH3

 C3H7Cl  H C Cl

CH3

372
 Mass Spectrum  Formula  Structure

How do we derive formula from the mass spectrum?

•m/z and relative intensities of M, M+1, and M+2

M: m/z = 78
C2H6O3
C3H7Cl
M C5H4N
C6H6
etc.

•A few useful rules to narrow the choices

373
 How Many Nitrogen Atoms?
Consider these molecules:
CH3 O
CH3
O2N NO2 H 3C N
N
NH3 H2NNH2
O N N

NO2 CH3

Formula: NH3 N2 H4 C7H5N3O6 C8H10N4O2

m/z (M): 17 32 227 194

Conclusion
•When m/z (M) = even, number of N in formula is even
•When m/z (M) = odd, number of N in formula is odd }
The Nitrogen Rule

374
 How Many Nitrogen Atoms?
A Nitrogen Rule Example

Example: Formula choices from previous mass spectrum

M: m/z = 78 m/z even

C2H6O3 even nitrogen count

C3H7Cl even nitrogen count

discarded C5H4N odd nitrogen count

even nitrogen count

C6H6

375
 How Many Hydrogen Atoms?

One pi bond Two pi bonds

HC C

C6H14 C6H12 C6H10

max H for 6 C H count = max - 2 H count = max - 4

Conclusion: Each pi bond reduces max hydrogen count by two

376
 How Many Hydrogen Atoms?

One ring Two rings

C6H14 C6H12 C6H10

max H for 6 C H count = max - 2 H count = max - 4

Conclusion: Each ring reduces max hydrogen count by two

377
 How Many Hydrogen Atoms?
One nitrogen Two nitrogens
NH2 NH2

NH2
CH3

N H3C N
N CH3

CH3

C6H14 C6H15N C6H16N2

max H for 6 C H count = max + 1 H count = max + 2

Conclusion:
•Each Nitrogen increases max H count by one
•The same for P, As, Sb, Bi
•No change in number of Hydrogen for O, S, Se,Te
•One Hydrogen subtract from saturated Hc for F, Cl, Br, I
•Ex. C2H6 C2H5F C2H4F2 378
 Index of Hydrogen Deficiency
• IHD = number of pairs • IHD = The SUM of the
of hydrogen that must number of rings, double
be removed from the bonds, or the number of
corresponding saturated triple bonds
hydrocarbon.

hydrogens and halogens nitrogens

IHD = C - H + N + 1
2 2
carbons
379
 For example
C6H12 C6H6
• IHD = 6 – 12/2 + 1 = 1 • IHD = 6 – 6/2 + 1 = 4
• There is 1 ring or double • There are 4 rings or double
bond. bonds or some combination
of both.
C5H9Br C3NH9
• IHD = 5 – 10/2 +1 = 1 • IHD = 3 – 9/2 + ½ + 1 = 0
• Ring or double bond • There are no rings or double
bonds.

380
 Mass Spectrum Formula
Example #1

m/z Molecular ion Relative abundance Conclusions

102 M 100% Mass (lowest isotopes) = 102
Given information

Even number of nitrogens

103 M+1 6.9% 6.9 / 1.1 = 6.3 Six carbons*

104 M+2 0.38% < 4% so no S, Cl, or Br

Oxygen?

*Rounding: 6.00 to 6.33 = 6; 6.34 to 6.66 = 6 or 7; 6.67 to 7.00 = 7

381
 Mass Spectrum Formula
Example #1

Mass (M) - mass (C, S, Cl, Br, F, and I) = mass (N, O, and H)
102 - C6 = 102 - (6 x 12) = 30 amu for N, O, and H

Oxygens Nitrogens 30 - O - N = H Formula Notes

0 0 30 - 0 - 0 = 30 C6H30 Violates hydrogen rule

1 0 30 - 16 - 0 = 14 C6H14O Reasonable

2 0 30 - 32 - 0 = -2 C6H-2O2 Not possible

0 2* 30 - 0 - 28 = 2 C6H2N2 Reasonable
*Nitrogen rule!
•Other data (functional groups from IR, NMR integration, etc.) further trims the list
382
 Mass Spectrum Formula
Example #2

m/z Molecular ion Relative abundance Conclusions

157 M 100% Mass (lowest isotopes) = 157
Odd number of nitrogens

158 M+1 9.39% 9.39 / 1.1 = 8.5

Eight or nine carbons

159 M+2 34% One Cl; no S or Br

383
 Mass Spectrum Formula
Example #2

Try eight carbons: M - C8 - Cl = 157 - (8 x 12) - 35 = 26 amu for O, N, and H

Oxygens Nitrogens 26 - O - N = H Formula Notes

0 1* 26 - 0 - 14 = 12 C8H12ClN Reasonable
*Nitrogen rule!

Not enough amu available for one oxygen/one nitrogen or no oxygen/three nitrogens

384
 Mass Spectrum Formula
Example #2

Try nine carbons: M - C9 - Cl = 157 - (9 x 12) - 35 = 14 amu for O, N, and H

Oxygens Nitrogens 14 - O - N = H Formula Notes

0 1* 14 - 0 - 14 = 0 C9ClN Reasonable
*Nitrogen rule!

Not enough amu available for any other combination.

385
386
387
Ex. Consider an unknown substance with a molecular mass of 94 amu.

According to the formula n=7 and r=3. The base formula must be C7H10
The index of hydrogen deficiency isU=

The formula must contain 3 ring or double bond.

388
• If we wish to add oxygen with the same mol.mass,
• the mol. Formula would become C6H6O.
 Base formula = C7H10 U=3
 Add: +O
 Subtract:-CH4
 Change the value of U: ∆U=1
 New formula = C6H6O
 New U: 4
The other possible molecular formulas with mole. Mass
of 94 amu are:
C5H202 U=5 C5H2S U=5
C6H8N U=3.5 CH3Br U=0

389
 Process of interpreting a mass spectrum
• MS allows one to determine the molecular weight of an
unknown compound if the M+· peak can be identified.
1. The nitrogen rule is the following:
 A compound has an odd molecular weight if and only if there are
an odd number of nitrogen atoms in its formula.
 The nitrogen rule holds for compounds containing H, C, N, O, Si, P,
S, or any of the halogens,
2. Every C-containing ion has a small peak accompanying it
that weighs one mass unit more.
 The ratio of the intensities of the (M) and (M+1) peaks is
directly proportional to the number of C atoms in the ion.
 The peak is due to small amounts of naturally occurring 13C,
which has 1.1% natural abundance.

390
• The intensity of the (M+1) peak allows one to
determine exactly of how many C atoms a particular
ion consists.
• For example, a C6 ion has a 6.6% probability of
having one 13C atom in it, so its (M+1) peak is 6.6%
of the intensity of the M+· peak.
• If no information about intensities of (M) and (M+1)
use Rule of Thirteen.
3. The presence and size of an M+2 peak tells you
whether Cl or Br atoms are present.
• Cl (75% 35Cl, 25% 37Cl) and Br (50% 79Br, 50% 81Br)

391
4. Calculate the degrees of unsaturation in your formula.
 You may have too few (fewer than zero, i.e. a negative
number) or too many degrees of unsaturation in your
compound.
 Too few degrees of unsaturation means that you have too
many H atoms.
a. If you have too few number of degrees of unsaturation, you
must add degrees of unsaturation, i.e. remove H’s without
changing the molecular weight.
 There are a few ways to do this.
I. Replace CH4 with O. This has the effect of adding one degree
of unsaturation.
II. Replace C2H4 with N2. This also has the effect of adding one
degree of unsaturation.
III. Replace H16 with O. This has the effect of adding eight degrees of
unsaturation

392
(b) If you have a very large number of degrees of
unsaturation, you may want to subtract degrees of
unsaturation.
– (Most of the compounds I would have you identify have 0–5
degrees of unsaturation.) Replace C with H12.
– This has the effect of subtracting seven degrees of unsaturation
without changing the molecular weight.
5. You now have your first reasonable formula for your
compound.
– Once you generate a reasonable formula, you may do the
replacements to generate new formulas with the same molecular
weight.
6. Draw at least one structure for each formula.
– It’s useful to remember that a six-membered ring with three
double bonds (e.g. a phenyl group, C6H5; or one or more N
atoms may replace CH groups in the ring) uses up four degrees
of unsaturation.
393
7. The molecular ion, unfortunately, is not always observed. One can
also gain information from the fragmentation pattern.
• The fragmentation pattern constitutes a kind of "fingerprint" for a
compound.
• Different structural isomers and even stereoisomers give
different fragmentation patterns, so the fragmentation pattern
can be used to distinguish different compounds that have the
same molecular formula.
• The fragmentation pattern also provides evidence for and
against certain structural elements in the unidentified compound.
If the major fragments can be identified, and if a reasonable
mechanism for their formation from the molecular ion can be
written, then this constitutes evidence that the parent ion has
been correctly identified.

394
• For example, when a fragment ion of M= 91
is observed, it is almost always the very
stable benzyl cation PhCH2+, suggesting
that a benzyl group is present in the
parent compound.
• Ethyl esters, RCO2Et, often show fragments M
– 45 (for the fragment RCO) and
• M – 73 (for the fragment R).

395
Example. The mass spectrum of a compound shows an M+·
peak at 124 amu and no M+2 peaks. Determine some
molecular formulas for this compound.
(1) Nitrogen Rule => even No of N
(2) It will be clear from the M+2 peak how many Cl or Br
atoms you have.
– For each Cl or Br atom, subtract 35 or 79 from the
molecular weight, and write Cl or Br in your formula. In
the present case, no Cl or Br atoms are present.
(3) Determine the base formula by rule of thirteen.
124/13 =9 + 7/13 n=9 r=7
– C9H16
(4) Calculate the degrees of unsaturation in your formula.
• U=(9-7+2)/2 =2
396
5. You now have your first reasonable formula for your compound.
Once you generate a reasonable formula, you may do the
following replacements to generate new formulas with the same
molecular weight.
– (a) Replace CH4 with O. (Adds a degree of unsaturation.)
– (b) Replace C2H4 with N2. (Adds a degree of unsaturation.)
– (c) Replace CO with N2. (Leaves degrees of unsaturation unchanged.)
• Thus:
• C9H16 C8H12O (Three degrees of unsaturation.)
• C8H12O C7H12N2 (Three degrees of unsaturation.)
• C8H12O C7H8O2 (Four degrees of unsaturation.)
• C8H12O C6H8N2O (Four degrees of unsaturation.)
• C6H8N2O C5H8N4 (Four degrees of unsaturation.)
• Etc.

397
6. Draw at least one structure for each formula. It’s
useful to remember that a six- membered ring
with three double bonds
• (e.g. a phenyl group, C6H5; or one or more N
atoms may replace CH groups in the ring) uses
up four degrees of unsaturation.
• More problems:
(1) 88 amu, no M+2.
(2) 119 amu, no M+2.
(3) 108 amu, and there’s an M+2 peak that is 1/3 the
size of M.

398
399
 Interpreting Mass-Spectral Fragmentation
Patterns
• The way molecular ions break down can produce
characteristic fragments that help in identification
– Serves as a “fingerprint” for comparison with known materials in
analysis (used in forensics)
– Positive charge goes to fragments that best can stabilize it

400
Mass Spectral Fragmentation of Hexane

• Hexane (m/z = 86 for parent) has peaks at m/z = 71,

57, 43, 29

401
Hexane

402
Practice Problem 12.2: methylcyclohexane or
ethylcyclopentane?

403
 Mass Spectral Cleavage Reactions of
Alcohols
• Alcohols undergo -cleavage (at the bond next to the
C-OH) as well as loss of H-OH to give C=C

404
Mass Spectral Cleavage of Amines
• Amines undergo -cleavage, generating
radicals

405
 Fragmentation of Ketones and
Aldehydes

• A C-H that is three atoms away leads to an

internal transfer of a proton to the C=O, called
the McLafferty rearrangement
• Carbonyl compounds can also undergo 
cleavage

406
Fragmentation of Ketones and
Aldehydes

407
 Mass Spectra
of Alkanes
More stable carbocations will be more
abundant.

=>
408
 Mass Spectra
of Alkenes
Resonance-stabilized cations favored.

=>
409
dodekan

410
4-metylundekan

411
2,2,4,6,6-pentametylheptan

412
dihexyleter

413
Vilken -klyvning ger det största fragmentet för
efedrin?

414
6-dodekanon

415
1-dodeken

416
3-metyl-3-hexanol

417