SPECTROSCOPY

The study of the interaction between matter and electromagnetic spectrum.

Spectroscopy is the scientific technique focused on studying matter through the
absorption, emission, or scattering of electromagnetic radiation, providing insights into
the composition and properties of substances.
SPECTOMETRY
Is a generation of interpretable data or spectra, from a lot of different techniques
including spectroscopy.

PRINCIPLE OF SPECTROSCOPY:
The principle of spectroscopy is the study of organic compounds using various
spectroscopic techniques to analyze their structure, composition, and properties.
Spectroscopy is a powerful analytical tool that provides valuable information about the
molecular structure of organic molecules by examining their interaction with
electromagnetic radiation.
1.Interaction with Electromagnetic Radiation
2.Energy Levels and Transitions
3.Types of Spectroscopic Techniques
 Infrared Spectroscopy (IR):
 Nuclear Magnetic Resonance Spectroscopy (NMR)
 Ultraviolet-Visible Spectroscopy (UV-Vis)
 Mass Spectrometry (MS)
Interaction with Electromagnetic Radiation: Spectroscopy focuses on how organic
compounds interact with electromagnetic radiation across different regions of the
electromagnetic spectrum, including ultraviolet, visible, infrared, and radio waves.
Energy Levels and Transitions: Spectroscopy involves transitions between energy levels
in organic molecules. The absorption or emission of electromagnetic radiation
corresponds to transitions between different energy states within the molecules,
providing insights into their electronic, vibrational, and rotational properties.
Infrared Spectroscopy (IR): Analyzes the vibrational modes of organic molecules,
providing information about functional groups and molecular structure.
Nuclear Magnetic Resonance Spectroscopy (NMR): Investigates the magnetic properties
of atomic nuclei in molecules, offering insights into connectivity and environment of
atoms.
Ultraviolet-Visible Spectroscopy (UV-Vis): Measures light absorption and transmission by
molecules, aiding in determining electronic transitions and identifying chromophores.
Mass Spectrometry (MS): Characterizes the mass and fragmentation patterns of
molecules, aiding in the identification and quantification of organic compounds.
USES
Spectroscopy techniques like IR, NMR, UV-Visible, Mass Spectrometry, and Fluorescence
are pivotal in organic chemistry for identifying functional groups, elucidating molecular
structures, studying electronic transitions, determining molecular weights, and analyzing
molecular interactions.
IMPORTANCE
Spectroscopy in organic chemistry is vital for determining molecular structures, verifying
compound purity, monitoring reactions in real-time, quantitatively analyzing organic
compounds, and identifying functional groups based on characteristic absorption or
emission patterns.

INTRODUCTION
• Infrared spectroscopy or vibrational spectroscopy is concerned with the study of
absorption of infrared radiation, which results in vibrational transitions.
• Infrared radiations refer broadly to that part of electromagnetic spectrum between
visible and microwave region.

PRINCIPLE
• When the frequency of the IR radiation is equal to the natural frequency of vibration,
the molecule absorbs IR radiation and a peak is absorbed.
• Every bond or portion of a molecule or functional group requires different frequency
for absorption.

THEORY
• IR radiation does not have enough energy to induce electronic transitions as seen with
UV.
• For a molecule to absorb IR, it must be accompanied by a change in dipole moment.
Diff • Regions of wavelength range There are three regions:
1. Very near IR: Overtone region (2 - 2.5μ)
2. Near IR: Vibration region(2.5 – 25μ)
3. Far IR: Rotational region(25 – 400μ)

TYPES OF VIBRATIONS
There are different types of vibrations:
1. Stretching
i. Symmetric
ii. Asymmetric
2. Bending
i. In-plane bending
a. Scissoring
b. Rocking
ii. Out-of-plane bending
a. Wagging
b. Twisting

FACTORS INFLUENCING VIBRATIONAL FREQUENCY

1. Symmetry
Symmetric compounds do not possess dipole moment and are IR inactive.
E.g. symmetric acetylene
2. Fermi resonance
Fermi resonance results in an unexpected shift in energy and intensity of the bands.
E.g. the overtone of C-H deformation mode at 1400 cm¹ is always in Fermi resonance
with the stretch of the same band at 2800 cm-1.
3. Hydrogen bonding
Hydrogen bonding brings about remarkable downward frequency shifts.
Intermolecular - broad bands
Intra-molecular - sharp bands
4. Electronic effect
Electronic effects such as inductive, mesomeric and field effect may cause shift in
absorption bands due to change in absorption frequency.
E.g. Inductive - acetone(1715cm¯¹) and chloroacetone(1725cm¯¹)
Mesomeric- acetophenone(1693cm¯¹) and p-amino acetophenone(1677cm¯¹)
5.Bond angles
Difference in bond angles also lead to the changes in absorption/ bands.

INSTRUMENTATION
The main parts of IR spectrometer are as follows :
1. IR radiation sources
2. Monochromators
3. Sample cells and sampling of substances
4. Detectors

1.IR radiation sources

 The radiation source must emit IR radiation which must be
(i) intense enough for detection
(ii) steady
(iii) extend over the desired wavelengths
 The various popular sources of IR radiations are :
(i) Incandescent lamp
(ii) Nernst glower
(iii) Globar Source
(iv) Mercury Arc
2.Monochromators

A. Prism:-
Used as dispersive element.
Constructed of various metal halide salts.
Sodium chloride is most commonly prism salt used.

B.Grating
Grating are nothing but rulings made on some materials like glass, quartz or
alkylhalides depending upon the instrument. The mechanism is that diffraction produces
reinforcement. The rays which are incident upon the gratings gets reinforced with the
reflected rays.
3.Sample cell & Sampling of substance
• Infrared spectra may be obtained for gases, liquids or solids.
• Materials containing sample must be transparent to the IR radiation. So, the salts like
NaCl, KBr are only used.
Sample handling
• Samples of the same substance shows shift in absorption bands as we pass from
solid to gases and hence the samples of different phases have to be treated differently
in IR spectroscopy.
• Sampling of solids
1. Solids run in solution
2. Mull technique
3. Pressed pellet technique
4. Solids films
1. Solids run in solution
Dissolve solid sample in non -aqueous solvent and place a drop of this solution in alkali
metal disc and allow to evaporate, leaving a thin film which is then mounted on a
spectrometer.
E.g. of solvents - acetone, cyclohexane, chloroform etc.
2. Mull technique
Finely powdered sample + mulling agent (Nujol) and make a thick paste (mull).
Transfer the mull to the mull plates and the plates are squeezed together to adjust the
thickness it is then mounted in spectrometer
3. Pressed pellet technique
Finely powdered sample is mixed with about 100 times its weight of KBr in a vibrating
ball mill and the mixture is then pressed under very high pressure in a die to form a
small pellet (1-2mm thick and 1cm in diameter).
4. Solid films Here amorphous solid is dissolved in volatile solvents and this solution is
poured on a rock salt plate (NaCl or KBr), then the solvent is evaporated by gentle
heating.
Sampling of liquids
Liquids sample can be sandwiched between two alkali halide plates (NaCl, KBr, CaF2).
The sample cell thickness is 0.01-0.05mm.
Sampling of gases
Here gases sample is introduced into a glass cell made up of NaCl.
Very few organic compounds can be examined as gases.
E.g.: 1, 4-dioxane
4.Detectors
Difficult • The detectors can be classified into three categories:
1. Thermal detectors:- Their responses depend the heating effect of radiation.
2. Pyroelectric detectors:- Pyroelectric effect depends on the rate of change of the
detector temperature rather than on the temperature itself.
3. Photoconducting detectors:- Most sensitive.

Dispersive IR instrument
• Dispersive IR instruments are introduced in 1940's. • Double-beam instruments are
mostly used than Single beam instrument. • In dispersive IR sequential scanning of
wave numbers of light takes place.
Fourier Transform IR Instrument
• FTIR collects all wavelengths simultaneously and at once.
• FTIR works based on Michelson Interferometer which having
(i) Beam splitter
(ii) Fixed mirror
(iii) Movable mirror
APPLICATIONS OF IR SPECTROSCOPY
1. Identification of an organic compound
To measure spectrums.
No two samples will have identical IR spectrum.
Fingerprint Region
•Absorption band in the region 1500-500 cm¯¹.
• Useful for establishing the identity of a compound.
It consists of :

1.Region 1500-1350 cm¯¹: Appearance of doublet near 1380 cm¹ and 1365cm¹ shows
the presence of 3º butyl group.
2. Region 1350-1000 cm¯¹: All classes of compound viz. alcohol, esters, lactones shows
absorptions in the region due to C-O stretching.
3. Region below 1000 cm¯¹: This region distinguishes between cis and trans alkene.

2.Qualitative determination of functional groups

• The presence or absence of absorption bands help in predicting the presence of
certain functional group in the compound.
3. Quantitative analysis
• It can be done by measuring the intensity of the absorption bands.
• This is done by baseline technique and is thus used to determine the quantity of a
substance.
4.Identifying the impurities in a drug sample
• Impurities have different chemical nature when compared to the pure drug.
• Hence these impurities give rise to additional peaks than that of the pure drug.
• By comparing these we can identify the presence of impurities.

LIMITATION OF INFRARED SPECTROSCOPY

• By IR spectroscopy, it is not possible to know the molecular weight of a substance.
• It does not provide information of the relative positions of different functional groups
on a molecule.
• From a single IR spectrum of an unknown substance, it is not possible to know
whether it is a pure compound or a mixture of compounds.

MASS SPECTROSCOPY
is the accurate method for determining of molecular mass of the
compound and its elemental composition.
PRINCIPLE OF MASS SPECTROSCOPY

when molecules are bombarded with an energetic electron

beam, 1e- is removed from the molecule.
Further fragmentation of molecular ions produces daughter
ions.
Different Terms Involved in the Mass Spectrum

A mass spectrum is a record of the masses and relative

abundances of the ions. The m/z ratios are taken along the
abscissa, while the relative abundances (intensity) are taken
along the ordinate.

Fig1: Mass spectrum of carbon dioxide

Base Peak
It is the highest peak or more intense peak in the spectrum.

Molecular Ion Peak

molecular ion is also called the parent ion/ and is usually
designated as M+., a positively charged molecule with an unpaired
electron.
Features of Molecular Ion Peak:

 The molecular ion peak in aromatic compounds is relatively much intense

due to the presence of a π-electron system.
 Conjugated olefines show a more intense molecular ion peak as compared
to the corresponding non-conjugated olefins with the same number of
unsaturation.
 Unsaturated compounds give a more intense peak as compared to
saturated or cyclic molecules.
 The relative abundance of molecular ion peaks of straight chain
compounds is more than the corresponding branched-chain compound
with the same number of carbon atoms.
 The absence of a molecular ion peak in the mass spectrum means that the
compound under examination is a highly branched or tertiary alcohol.

Fragment Ion Peak

the ions formed by the fragmentation of molecular ions or other ions
in a mass spectrometer give a different peak in the mass spectrum
these are called fragment ion peaks.

Metastable Ion
the ions that fragment slowly after the emergence from the ion
source but before they reach the detector. They are thus displaced
from the position in the mass spectrum, which would correspond to
their true masses.
If the ions (molecular or fragment) M+ are accelerated before their
breakdown then they may decompose in the accelerating chamber
into M2+ and M3, and part of the kinetic energy of M1+ is lost to the
neutral fragment M3. M2+ is continuous to accelerated and collected.
M2+ produced in this way is not recorded as mass M2 but recorded as M*,
where M*= M22/M1
M* is called metastable ions and is usually recorded as a weak broad peak of low
intensity.

Characteristics of Peaks
 They don’t necessarily occur at the integral m/z value.
 These are much broader than the normal peaks.
 These are of relatively low abundance.

Nitrogen Rule
 Nitrogen-containing compounds with an odd number of nitrogen atoms in
the molecule must have an odd molecular mass. An even number of
nitrogen atoms or the absence of nitrogen in the molecule show the
molecular mass of the compound must be even.

General Fragmentation Modes.

 Stability of ions
 Stability of radical lost the stability of the ions can be judged by stabilization
of the charge, which depends upon;

a. Resonance
b. Inductive effect
c. Polarisability and so on
Important Fragmentation Modes

Simple Cleavage
Fragmentation of odd electron molecular ion M+. may occur through
homolytic or heterolytic cleavage of single bond.

A. Homolytic Cleavage

Odd electron ions have an unpaired electron which is capable of new

bond formation. The energy released by bond formation can help
offset the energy required for the cleavage of some other bond in the
molecules.

Homolytic Cleavage Reactions Classified as:

Mode I:
This type of fragmentation mode operates in compounds in which
the heteroatom is singly bonded to a carbon atom.
 More abundant peaks are formed by the cleavage of the C-C bond,
which is in the α position to the heteroatom in mass spectra of
alcohol, amines, and ethers.

Mode II
when a heteroatom is bonded to the carbon atom by the double
bond, α-cleavage is the preferred fragmentation mode.

B. Heterolytic Cleavage

Cleavage of the C-X (x= O, N, S, Cl) bond is more difficult than that of
the C-C bond. In such a cleavage the positive charge is carried by the
carbon atom and not by a heteroatom.

Retro-Diel’s Alder Reaction

 It is the characteristic of cyclic olefins, which involve multicentered
fragmentation. It involves the cleavage of two bonds of the cyclic
system resulting in the formation of two stable unsaturated
fragments in which two new binds are formed..
The highly substituted or more conjugated fragment, which has low
ionization energy, carries a charge.

Rearrangement Reactions
fragments whose origin can’t be described by simple cleavage of bond in
the molecular ion but are a result of intramolecular atomic rearrangement
during fragmentation.
 Rearrangement resulting in the elimination of stable neutral molecules is
common.
 The rearrangement peak can be recognized by considering the m/z
number of fragments ions and their corresponding molecular ion.
 An even-numbered peak derived from even-numbered molecular ions is
the result of two cleavages, which may involve a rearrangement.

Different Modes of Rearrangements

A. Hydrogen Transfer

these processes are very common in mass spectroscopy, which involves

the transfer of hydrogen atoms from one part of the molecule to another
part.
.
B. γ -Hydrogen Transfer (Mc-Lafferty
rearrangement)
involves the cleavage of the β-bond followed by the γ-Hydrogen transfer.
The mechanism involves the six-membered transition state. This
rearrangement eliminates neutral molecules from aldehydes, ketones,
amines, and unsaturated compounds.

To undergo the Mc-Lafferty rearrangement reaction, a molecule must

possess appropriately located heteroatoms (e.g., oxygen), a π system, and
an abstractable hydrogen atom at γ position to the C=O system.

MC-
Lafferty rearrangement reaction
C. Random Rearrangement
hydrocarbon was noted by early mass spectrometers in the
petroleum industry.

The mass spectrometer is generally designed to perform three basic functions,

they are:
 To vaporize the compounds of various volatility.
 produce ions from the neutral compounds in the vapor phase.
 To separate the compounds according to their mass-to-charge ratio and
record them.

Instrumentation of Mass Spectrometry (MS)

Sample handling system

🎯The sample handling system is used to introduce the sample into the ion source at low pressure.

-🎯Heating is required for less volatile sample.

🎯Solid, liquid, and gas diff /samples can be used in mass spectrometry.
Ionization process in Mass Spectrometry

🎯Samples are ionized by removing one or more electrons to give the molecular ions and fragment ions.

Different Ionization methods used in Mass spectroscopy:

Electron ionization/Electron impact

🎯This is the oldest and best-characterized method of ionization.

🎯 In this process, the beam of electrons passes through the gas sample.

🎯 The electrons collide with the neutral molecule and knock off another electron to form molecular ions
or fragment ions.

Chemical ionization

🎯The chemical ionization process involves reagent gas like methane, isobutane or ammonia.

🎯First, the reagent gas is ionized by electron impact, and the reaction between reagent gas ions and the
sample produces the ions of the analyte.
Field desorption

🎯In this process, the sample is placed on the anode of pair of electrodes, and the electrodes are placed at
too high a potential.

🎯SO, the sample desorption occurs to produce molecular and quasimolecular ions with sufficient internal
energy for extensive fragmentation.

Atmospheric pressure chemical ionization (APCI)

🎯In APCI, a corona discharge is used to ionize the sample in the atmospheric region.

🎯The gas phase ionization in APCI is more effective for analyzing less-polar species.

Fast atom bombardment (FAB)

🎯It involves the bombarding of samples by using beams of xenon atoms of high transitional energy. In
this process, xenon atoms are first ionized by using the electrons to give xenon radical cations.

🎯The xenon radical cations are accelerated to 6-10 keV to give radical cations of high transitional energy.

🎯The radical cations are then passed through xenon to form the high-energy xenon atom Xe and Xe.+ions
are removed by the electric field.

🎯The compounds of interest are placed in a metal sheet and ionized by a high-energy beam of a xenon
atom.

Electrospray ionization

🎯The electrospray ionization involves placing the ionizing voltage across the nebulizer needle present at
the outlet from high-performance liquid chromatography.

🎯ESI can produce the multiply charged ions with the number of charged tending to increase with an
increase in molecular weight.

🎯 This is popularly used for water-soluble biomolecules like protein, peptides, and carbohydrates.

Matrix-assisted laser desorption ionization

🎯In this process, the sample is dissolved in the solution containing an excess of a matrix like dihydroxy
benzoic acid, and sinapic acid, which consists of chromophores, capable of absorbing laser light.

🎯When the solution is placed in the laser light the solution absorbs the laser light and produces plasma,
which results in ionization and vaporization of the sample.

Acceleration of ions

🎯Ions are accelerated to attain the same kinetic energy.

🎯The ions pass through three accelerating slits with decreasing voltage.

Deflection of ions

🎯Ions are deflected by using the magnetic field on the basis of their m/z ratio.

🎯The lighter ions with a high positive charge are more deflected than others.

Mass analyzers of Mass Spectrometry

Different mass analyzers are:

Quadrupole mass filter

🎯Qurdupole mass filter consists of four cylindrical rods arranged in squares parallel to the direction of the
ion beams.

🎯In this radiofrequency and direct current are applied.

🎯The combination of Rf and direct current generates the oscillating electrostatic field between the region
of ions.

🎯When the ions enter into the mass analyzer depending upon the ratio of Rf and Dc voltage oscillating
electrostatic field will be generated for ions.

🎯Ions with an inappropriate m/z ratio will undergo an unstable oscillation and hit the rods.

🎯But ions with the correct m/z ratio undergo stable oscillation and strike the detector to give a signal.
Quadruple ion trap:

🎯It is the spherical configuration of a linear mass filter.

🎯The difference between a linear mass filter and an ion trap is that the linear mass filter directs sorted
ions through the detector, whereas the ion trap temporarily retains unsorted ions within the trap.

🎯After scanning the electric field, they are released to the detector.

🎯Because of their speed and sensitivity, quadrupole ion trap methods are well suited for use with
capillary gas chromatography.

🎯These are compact, inexpensive, and easy to use.

Time of flight mass spectrometer

🎯In this procedure, ions are subjected to a high potential difference (V) to attain the same transitional
energy in electron volt.

🎯They are further accelerated and transferred to the field-free region.

🎯There they are separated overtime on the basis of their m/z values.

🎯 This is simply based on the principle that the velocities of two ions depend on the mass of ions.

🎯In this process, ions should be created at the same instant and they should have the same kinetic
energy.
🎯The lighter ions have higher velocity compared to the higher ions, so on passing towards the detector,
they hit the detectors first.

Fourier transform-Ion Cyclotron Resonance

🎯Ions, generated by the electron beam from heated filament are passed into cubic cells under vacuum
conditions.

🎯An electric tapping potential and a magnetic field hold these ions in place.

🎯Depending on their m/z ratio, each ion assumes the cycloidal orbit at its own characteristic frequency.

🎯By varying the electric field, these frequencies are scanned until the cycloidal frequency is in resonance
with the applied radio frequency.

🎯The motion of ions with the same frequency is coherent at resonance, and a signal is detected.

Detectors of Mass Spectrometry

Photoplate detectors

🎯It is the earliest and the largest ion detector.

🎯 It involves the dispersion of ions along the lengthy focal plane resulting in adequate unit mass
resolution across the entire spectral region.

🎯So photo plate detector makes able to have simultaneous detection and signal integration.

Electron multipliers

🎯The ions emerging from the mass analyzer are detected using an electron multiplier.

🎯It is a common type of ion detector that comes in a variety of designs.

🎯In this detector, ions striking the conversion dynode generate secondary ions.

🎯The dynodes then generate the electron cascade, effectively multiplying the single incident ions by 106
or more.

🎯The degree of multiplication is determined by the individual dynode surface composition, acceleration
per stage (bias voltage), the number of dynodes (6-20), and bias current circuit design.

Photomultiplier

🎯Ions strike the photomultiplier detector, resulting in electron emission.

🎯 The emitted electron then strikes the phosphor screen, giving rise to photons.

🎯After that, the photons are amplified by passing through the multiplier.

🎯The advantage of this detector is that it operates in a vacuum state, which prevents contamination and
extends the detector’s lifetime.

Faraday cups
🎯The name faraday cup is named after Michael Faraday.

🎯In this detector, a metal cup is placed in the path of the ion beam and is connected to an electrometer
that measures the current of the ion beam.

🎯When the incident ions strike the dynode surface, it produces electrons and induces a current, which is
amplified and recorded.

🎯 Faraday cups can detect the higher current, which cannot be measured by an electron multiplier.

Photographic plates

🎯These are the time integrating devices generally used with the radiofrequency spark instruments.

🎯Photographic plates integrate the ion signal over time and detect the ions of all masses simultaneously.

🎯It is the simplest and oldest type of ion detector.

(watch video)

Application of Mass Spectroscopy

🎯It is used to determine the molecular weight of compounds.

🎯In organic chemistry, mass spectroscopy is used to determine the structure of complicated compounds.

🎯Mass spectroscopy is used for the qualitative and quantitative study of compounds.

🎯It is also used for the detection of impurities.

🎯Mass spectroscopy is used in the study of drug metabolism study, and also has clinical, -toxicological,
and forensic applications.

🎯It is used in the isotope ratio determination and carbon dating process.

References:

Silverstein, R. M., Webster, F. X., & Kiemle, D. J. (2005). Spectrometric identification of organic
compounds. Hoboken, NJ: John Wiley & Sons.
Analytical_Chemistry/Supplemental_Modules_(Analytical_Chemistry)/Instrumental_Analysis/
Mass_Spectrometry/Mass_Spectrometers_(Instrumentation)/Mass_Analyzers_(Mass_Spectrometry)

http://www.premierbiosoft.com/tech_notes/mass-spectrometry.html

https://barclayphysics.fandom.com/wiki/How_are_the_ions_produced_and_detected

https://byjus.com/chemistry/mass-spectrometry/

https://microbenotes.com/mass-spectrometry-ms-principle-working-instrumentation-steps-
applications/

https://pubs.acs.org/doi/pdf/10.1021/ac053495p

https://www.britannica.com/science/mass-spectrometry/Hydrogen-carbon-nitrogen-oxygen-and-sulfur-
in-nature

https://www.chemguide.co.uk/analysis/masspec/howitworks.html

https://www.priyamstudycentre.com/2022/02/mass-spectrometry.html

https://www.researchgate.net/publication/328661548_Mass_Spectrometry_Detectors_Review

https://www.technologynetworks.com/analysis/articles/types-of-ion-detector-for-mass-spectrometry-
347890

https://www.technologynetworks.com/analysis/lists/eight-emerging-applications-of-mass-spectrometry-
288234

https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/spectrpy/massspec/masspec1.htm

https://scienceinfo.com/mass-spectroscopy/

UV-Vis Spectroscopy

Ultraviolet and visible spectroscopy deals with the recording of the absorption of
radiations in the ultraviolet and visible regions of the electromagnetic spectrum. The
ultraviolet region extends from 10 to 400 nm. It is subdivided into the near ultraviolet
(quartz) region (200-400 nm) and the far or vacuum ultraviolet region (10-200 nm).
The visible region extends from 400 to 800 nm.
The absorption of electromagnetic radiations in the UV and visible regions induces the
excitation of an electron from a lower to higher molecular orbital (electronic energy
level). Since UV and visible spectroscopy involves electronic transitions, it is often called
electronic spectroscopy. Organic chemists use ultraviolet and visible spectroscopy
mainly for detecting the presence and elucidating the nature of the conjugated multiple
bonds or aromatic rings.
The visible region of the spectrum (visible to the human eye, that is) corresponds to
light with wavelengths of 400 to 800 nanometers (nm; 1nm = 10 meters). Ultraviolet
light has a shorter wavelength, about 200 nm IR light has a longer wavelength 2500
nm. Older units for reporting these spectra are millimicrons (mu; 1m*mµ = 1nm ) or
angstrom units (Å / 10 Å = 1nm) .
The amounts of energy associated with light are 37 kcal/mol to 75 kcal/mol for the
visible region and 75 kcal/mol to 150 kcal/mol for the ultraviolet region. These energies
are much larger than those involved in IR spectroscopy (2 to 12 kcal/mol). They
correspond to the amounts of energy needed to cause an electron to jump from a filled
molecular orbital to a higher-energy, vacant molecular orbital. Such electron jumps are
called electronic transitions.
Visible (vis) 400-800 nm (or mµ) 4000-8000 Å
Ultraviolet (uv) 200-400 nm for mµ) 2000-4000 Å
I nanometer (ran) = 10 meters
1 millimicron (mµ) = 1nm
10 angstroms (Å) = 1nm
A visible-ultraviolet spectrum records electronic transitions. Electron jumps from filled
molecular orbitals to higher energy vacant molecular orbitals.
Visible (vis) 400-800 nm (or mµ) 4000-8000 Å
Ultraviolet (uv) 200-400 nm for mµ) 2000-4000 Å
I nanometer (ran) = 10 meters
1 millimicron (mµ) = 1nm
10 angstroms (Å) = 1nm
A visible-ultraviolet spectrum records electronic transitions. Electron jumps from filled
molecular orbitals to higher energy vacant molecular orbitals.
The band at shorter wavelength corresponds to a pi electron transition, whereas the
longer-wavelength, weaker-intensity band corresponds to a transition of the non-
bonding electrons on the carbonyl oxygen atom. The intensity of an absorption band
can be expressed quantitatively. Band intensity depends on the particular molecular
structure and also on the number of absorbing molecules in the light path.
Absorbance, which is the log of the ratio of light intensities entering and leaving the
sample, is given by the equation :
A=εcl (Beers law)
where ε is the molar absorptivity (sometimes called the extinction coefficient), c is the
concentration of the solution in moles per liter, and I is the length in centimeters of the
sample through which the light passes. The value of e for any peak in the spectrum of a
compound is a constant characteristic of that particular molecular structure.
For example, the values of e for the peaks in the spectrum of the unsaturated ketone
shown in figure are ƛ max =232 nm (ε= 12, 600) and ƛ max =330 nm (ε= 78)
If it absorbs ultraviolet light, a UV spectrum is obtained; if it absorbs visible light, a
visible spectrum is obtained. Ultraviolet light is electromagnetic radiation with
wavelengths ranging from 180 to 400 nm (nanometers); visible light has wavelengths
ranging from 400 to 780 nm.
(One nanometer is or 10 Å.) Wavelength is inversely related to the energy: The shorter
the wavelength, the greater is the energy. Ultraviolet light, therefore, has greater
energy than visible light.
E = hc h
h =Planck’s constant
c= velocity of light
= wavelength
The normal electronic configuration of a molecule is known as its ground state—all the
electrons are in the lowest-energy molecular orbitals. When a molecule absorbs light of
an appropriate wavelength and an electron is promoted to a higher energy molecular
orbital, the molecule is then in an excited state. Thus, an electronic transition is the
promotion of an electron to a higher energy MO. The relative energies of the bonding,
nonbonding, and antibonding molecular orbitals are shown.
Ultraviolet and visible light have sufficient energy to cause only the two electronic
transitions. The electronic transition with the lowest energy is the promotion of a
nonbonding (lone-pair) electron (n) into a antibonding molecular orbital. This is called
an (stated as ―n to star‖) transition.
The higher energy electronic transition is the promotion of an electron from a bonding
molecular orbital into a antibonding molecular orbital, known as a (stated as ― to star‖)
transition. This means that only organic compounds with electrons can produce UV Vis
spectra.