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Spectroscopic Techniques

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

Department of Chemistry Bangladesh University of Engineering


& Technology (BUET)
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)

Department of Chemistry Bangladesh University of Engineering


& Technology (BUET)
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

Department of Chemistry Bangladesh University of Engineering


& Technology (BUET)
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

Department of Chemistry Bangladesh University of Engineering


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Nature of electromagnetic radiation

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


& Technology (BUET)
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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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.

Department of Chemistry Bangladesh University of Engineering


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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
Department of Chemistry Bangladesh University of Engineering
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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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Department of Chemistry Bangladesh University of Engineering
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Department of Chemistry Bangladesh University of Engineering
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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

Department of Chemistry Bangladesh University of Engineering


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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

Department of Chemistry Bangladesh University of Engineering


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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
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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
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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
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Department of Chemistry Bangladesh University of Engineering
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