Absorption Spectroscopy From 160 NM To 780 NM Measurement of Transmittance

Ultraviolet-Visible Spectroscopy
• Introduction to UV-Visible
 Absorption spectroscopy from 160 nm to 780 nm
 Measurement of transmittance
 Conversion to absorbance
* A=-logT=bc
• Measurement of transmittance and absorbance

• Beer’s law
• Noise
• Instrumentation
8-1
Measurement
• Scattering of light
 Refraction at interfaces
 Scatter in solution
 Large molecules
 Air bubbles
• Normalized by comparison to reference cell
 Contains only solvent
 Measurement for transmittance is
compared to results from reference cell
8-2
Beer’s Law
• Based on absorption of light by a
sample
 dPx/Px=dS/S
 dS/S=ratio of absorbance area
P n
to total area dP adn
 x

* Proportional to number of Po
Px 0
S
absorbing particles Po an
 ln 
 dS=adn P S
* a is a constant, dn is number Po an
log 
of particles P 2.303S
 n is total number of particles
within a sample
8-3
Beer’s Law
• Area S can be described by volume and length
 S=V/b (cm2)
Po anb
 Substitute for S log 
P 2.303V
 n/V = concentration
 Substitute concentration and collect
constant into single term 
• Beer’s law can be applied to mixtures
 Atot=Ax
8-4
Beer’s Law Limitations
• Equilibrium shift
 pH indicators
 Need to consider
speciation
 Weak acid
equilibrium
8-5
Beer’s Law Limitation
• Polychromatic Light
 More than one
wavelength
8-6
Noise
• Limited readout resolution
• Dark current and electronic noise
• Photon detector shot noise
• Cell position uncertainty
 Changing samples
• Flicker
8-7
Instrumentation
• Light source
 Deuterium and hydrogen lamps
 W filament lamp
 Xe arc lamps
• Sample containers
 Cuvettes
 Plastic
 Glass
 Quartz
8-8
Spectrometers
8-9
Spectrometer
Time separated double beam
8-10
Spectrometer
Dip probe
Multichannel photodiode array
8-11
Application of UV-Visible Spectroscopy
• Identification of inorganic and organic species

• Widely used method
• Magnitude of molar absorptivities

• Absorbing species
• methods
8-12
Molar Absorptivties
• Range from 0 to 1E5
 =8.7E19PA
 P=transition probability
 A=target cross section (cm2)
* Allowed transitions 0.1>P>1
 range 1E4 to 1E5
* Forbidden transition 0.01
• Absorbing species
 M+->M*
 M* has a short lifetime (nanoseconds)
 Relaxation processes
* Heat
* Photo emission
Fluorescence or phosphorescence
8-13
Absorbing species
• Electronic transitions
 and n electrons
 d and f electrons
 Charge transfer reactions
 and n (non-bonding) electrons
8-14
Sigma and Pi orbitals
8-15
Electron transitions
8-16
Transitions
 
 UV photon required, high energy
 Methane at 125 nm
 Ethane at 135 nm
• n-> 
 Saturated compounds with unshared e-
 Absorption between 150 nm to 250 nm
  between 100 and 3000 L cm-1 mol-1
 Shifts to shorter wavelengths with polar
solvents
* Minimum accessibility
 Halogens, N, O, S
8-17
Transitions
• n->, 
 Organic compounds, wavelengths 200 to
700 nm
 Requires unsaturated groups
 n->low  (10 to 100)
* Shorter wavelengths
 higher  (1000 to 10000)
8-18
Solvent effects
8-19
Transitions
• d-d
 3d and 4d 1st and 2nd transitions series
 Broad transitions
 Impacted by solution
8-20
Transitions
8-21
D transitions
• Partially occupied d orbitals
 Transitions from lower to higher energy
levels
 Splitting of levels due to spatial
distribution
similar
Axial direction
8-22
D transitions
• Binding ligands on axis have greater effect on
axial orbitals
8-23
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
8-24
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 8-25
Charge-transfer Transitions
• Electron donor and acceptor characteristics
 Absorption involves e- transitions from
donor to acceptor
 SCN to Fe(III)
* Fe(II) and neutral SCN
 Metal is acceptor
 Reduced metals can be exception
8-26
Electronic Spectra
• Cr(NH3)63+
 d3
 Weak low energy transition
 Spin forbidden
 2 stronger transitions
 Spin allowed
* t2g and eg
transitions
Lower
energy to
higher
energy
 CT at higher energy
 Ligand to metal
transition
8-27
Charge transfer bands
• High energy absorbance
 Energy greater than d-d
transition
 Electron moves between
orbitals
* Metal to ligand
* Ligand to metal
 Sensitive to solvent
• LMCT
 High oxidation state metal ion
 Lone pair ligand donor
• MLCT
 Low lying pi, aromatic
 Low oxidation state metal
 High d orbital energy
8-28
Solvent effect
8-29
Methods
• Titration
 Change of absorbance with solution
variation
 pH, ligand, metal
• Photoacoustic effect
 Emission of sound
8-30

Absorption Spectroscopy From 160 NM To 780 NM Measurement of Transmittance

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Absorption Spectroscopy From 160 NM To 780 NM Measurement of Transmittance

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Ultraviolet-Visible Spectroscopy

• Measurement of transmittance and absorbance

Time separated double beam

Multichannel photodiode array

• Identification of inorganic and organic species

• Magnitude of molar absorptivities

Figure 2: UV-vis spectra of organic phases for 13M

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