Spectroscopic Techniques

Dr Md Elius Hossain
Assistant Professor
Department of Chemistry
BUET, Dhaka-1000

Department of Chemistry Bangladesh University of Engineering

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 What is spectroscopy?

 Spectroscopy is the study of the properties of matter

through its interaction with the electromagnetic radiation

 We observe the interaction of light with different degrees

of freedom of the molecule. Each type of spectroscopy
involves different light frequency, and hence gives a
different picture (spectrum)

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 Objectives?

 how we can use this interaction of light with matter and

quantitatively understand our sample

 how we can use spectroscopy as a set of tools to

understand systems and solve chemical problems

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 Nature of electromagnetic radiation

 Electromagnetic radiation is a simple harmonic wave of

electric and magnetic fields fluctuating orthogonal to each
other

 Consists of particles called photons

 Propagates as waves

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 Nature of electromagnetic radiation

 Each photon has a characteristic wavelength and a

corresponding frequency

  = energy of a photon = h

 Intensity of radiation  density of photons

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 Nature of electromagnetic radiation

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 What is white source of radiation?

A source which emits radiation of all frequencies in a

certain range is called a white source

The Electromagnetic Spectrum

Visible light

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 Radiation Frequency range Source
(Hz)
RF 106-108 Oscillator circuit

Microwave 109-1011 Klystron

Infra-red 1013 Heated ceramic

element
Visible 1014 Tungsten lamp

UV 1015 D2 Discharge

X-rays 1017 Metals struck be

electrons

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 What does a spectrum measure?

 Interaction of light with a sample can influence the

sample and/or the light

 Process involves (1) excitation followed by (2) decection

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  In most spectroscopies, we characterise how a sample
modifies light entering it

Absorption: Change in intensity I of incident light

 Absorbance = log (Io/It)

 Transmittance (%) = (I/Io)x100

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Why do chemical species absorb or emit radiation of only
certain frequencies ?

 A molecule can possess energies in different forms such as

vibrational, rotational, electronic, translational energy

 Electronic (all species)

 Vibrational (molecules)
 Rotational (molecules in the gaseous state)
 Translational (all species in the liquid and gaseous state)

 Energy of a species = elec + vib + rot + tr

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Energy Level Diagram

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  Each type of energy of species is quantized, i.e. only
discrete values are possible

 A molecule can jump from one

energy level to another by
absorbing or emitting a photon
of energy that separate the two
energy levels

 Species can absorb photons, only if the energy of the

photon corresponds to the energy gap between quantum
states, subject to certain selection rules
E = hv

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 Ground state of chemical species

Under ordinary conditions, chemical species are-

In various rotational levels (if gaseous of course)

of the ground vibrational level (v = 0)

of the ground electronic state

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 UV-Visible or Electronic Spectroscopy

 Absorption of ultraviolet (UV) and visible radiation

 Species in the ground electronic state absorb photons

visible or uv radiation and undergo transition to upper
electronic states

 The corresponding spectrum: Electronic spectrum, or UV-

visible spectrum

 Applications of electronic spectroscopy includes:

identification (qualitative) and quantitative analysis,
structure determination

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 Electronic Transitions

 Diatomic molecules: transitions from the ground state to

several excited states are often observed

 Organic compounds: transition of bonding electrons or

non-bonding electrons to anti-bonding molecular orbitals

 Transition metal ions: d-d transitions, f-f transitions and

charge-transfer transitions

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 Quantitative Analysis

 Quantitative Analysis is based on the relation of absorbing

capacity of chemical species with their concentration in a
sample given by the Beer-Lambert law

A =  cl
A = absorbance = log(Io/It)
 = molar absorption coefficient
c = molar concentration
L = path length

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 Electronic Transitions

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 UV-Visible spectra of polyatomic organic molecules

 Broad bands are usually observed

 In liquids, high collision rate decreases life time, and

also deforms the excited state to increase the
uncertainty in the energy

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 ss* Transitions
 An electron in a bonding s orbital is excited to the
corresponding antibonding orbital

 The energy required is large. For example, methane

(which has only C-H bonds, and can only undergo s
 s* transitions) shows an absorbance maximum at
125 nm

 Absorption maxima due to s  s* transitions are not

seen in typical UV-Vis. spectra (200 - 700 nm)

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 n s* Transitions

 Saturated compounds containing atoms with lone

pairs (non-bonding electrons) are capable of ns*
transitions

 These transitions usually need less energy than

ss* transitions

 They can be initiated by light whose wavelength is in

the range 150-250 nm. The number of organic
functional groups with ns* peaks in the UV region
is small.

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 n * and * Transitions
 Most absorption spectroscopy of organic compounds
is based on transitions of n or  electrons to the *
excited state

 This is because 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  electrons
 Molar absorptivities from n  * transitions range from
10 to100 L mol-1 cm-1 .
   * transitions normally between 1000 and 10,000
L mol-1 cm-1
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 n * and * Transitions

 The energetically most favorable π  π* excitation

occurs from the highest energy bonding pi-orbital
(HOMO) to the lowest energy antibonding pi-orbital
(LUMO)

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 Solvent Effect: Increase in solvent polarity

* transitions (red shift)

 attractive polarisation forces between the solvent and the
absorber
 lowers the energy levels of both the excited and
unexcited states
 This effect is greater for the excited state, and so the
energy difference between the excited and unexcited
states is slightly reduced - resulting in a small red shift

 Peaks shifted by about 10-20 nm if ethanol replaces

hexane

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 Solvent Effect: Increase in solvent polarity

n * (blue shift)

 This arises from increased solvation of the lone pair,

which lowers the energy of the n orbital

 For acetone: 279 nm in hexane, 264.5 in aqueous

solution

 Carbonyl group can form hydrogen bond; lowers the

energy of n orbital (lesser extent)

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 Delocalised electrons

 Delocalisation of electrons results in an increase in the

length of region over which the electrons can move
around

 Quantum mechanical calculations show that

the spacing in energy levels decrease as a
result of this increase.

 The transition energy for HOMO to LUMO decreases

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 Conjugation of double bonds: red shift

 The longer the conjugated system, the higher is the

wavelength of the peaks

 Each additional double bond in the conjugated pi-

electron system shifts the absorption maximum about
30 nm in the same direction

 Moreover, the molar absorptivity (ε) roughly doubles

with each new conjugated double bond.

 extending conjugation generally results in

bathochromic and hyperchromic shifts in
absorption

Department of Chemistry Bangladesh University of Engineering

& Technology (BUET)
Department of Chemistry Bangladesh University of Engineering
& Technology (BUET)
Department of Chemistry Bangladesh University of Engineering
& Technology (BUET)
Department of Chemistry Bangladesh University of Engineering
& Technology (BUET)
Department of Chemistry Bangladesh University of Engineering
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Department of Chemistry Bangladesh University of Engineering
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Department of Chemistry Bangladesh University of Engineering
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 ELECTRONIC SPECTRA OF COMPLEXES

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Department of Chemistry Bangladesh University of Engineering
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Department of Chemistry Bangladesh University of Engineering
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Department of Chemistry Bangladesh University of Engineering
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Department of Chemistry Bangladesh University of Engineering
& Technology (BUET)
Department of Chemistry Bangladesh University of Engineering
& Technology (BUET)