Ultraviolet-Visible Spectroscopy

Introduction to UV-Visible l Absorption spectroscopy from 160 nm to 780 nm l Measurement of transmittance Conversion to absorbance * A=-logT= bc Measurement of transmittance and absorbance Beers law Noise Instrumentation

8-1

Measurement
Scattering of light l Refraction at interfaces l Scatter in solution Large molecules Air bubbles Normalized by comparison to reference cell l Contains only solvent Measurement for transmittance is compared to results from reference cell
8-2

Beers Law
Based on absorption of light by a sample l dPx/Px=dS/S dS/S=ratio of absorbance area P n dPx adn to total area = Px S P 0 * Proportional to number of absorbing particles Po an ln = dS=adn P S Po an * a is a constant, dn is number log = of particles P 2.303S l n is total number of particles within a sample
o

8-3

Beers Law
Area S can be described by volume and length l S=V/b (cm2) Po anb log = l Substitute for S P 2.303V l n/V = concentration l Substitute concentration and collect constant into single term Beers law can be applied to mixtures l Atot=Ax
8-4

Beers Law Limitations

Equilibrium shift l pH indicators Need to consider speciation Weak acid equilibrium

8-5

Beers Law Limitation

Polychromatic Light l More than one wavelength

8-6

Noise
Limited readout resolution Dark current and electronic noise Photon detector shot noise Cell position uncertainty l Changing samples Flicker

8-7

Instrumentation
Light source l Deuterium and hydrogen lamps l W filament lamp l Xe arc lamps Sample containers l 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 l =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 l M+ ->M* M* has a short lifetime (nanoseconds) Relaxation processes * Heat * Photo emission Fluorescence or phosphorescence
8-13

Absorbing species
Electronic transitions l , , and n electrons l d and f electrons l Charge transfer reactions , , and n (non-bonding) electrons

8-14

Sigma and Pi orbitals

8-15

Electron transitions

8-16

Transitions
> l UV photon required, high energy Methane at 125 nm Ethane at 135 nm n-> l 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 l Halogens, N, O, S
8-17

Transitions
n->, > l Organic compounds, wavelengths 200 to 700 nm l Requires unsaturated groups n-> low (10 to 100) * Shorter wavelengths > higher (1000 to 10000)

8-18

Solvent effects

8-19

Transitions
d-d l 3d and 4d 1st and 2nd transitions series l Broad transitions Impacted by solution

8-20

Transitions

8-21

D transitions
Partially occupied d orbitals l 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 l <Br-<Cl-<F-<OH-<C2O42-~H2O<SCN<NH3<en<NO2-<CNl increases with increasing field strength f-f l 4f and 5f (lanthanides and actinides) l Sharper transitions

8-24

Actinide transitions
5

Pu (835 nm)
4

6+

Pu (489 nm) Normal Heavy Light

4+

Absorbance

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 l Absorption involves e- transitions from donor to acceptor SCN to Fe(III) * Fe(II) and neutral SCN l Metal is acceptor Reduced metals can be exception

8-26

Electronic Spectra
Cr(NH3)63+ l d3 l Weak low energy transition Spin forbidden l 2 stronger transitions Spin allowed * t2g and eg transitions Lower energy to higher energy l CT at higher energy Ligand to metal transition

8-27

Charge transfer bands

High energy absorbance l Energy greater than d-d transition Electron moves between orbitals * Metal to ligand * Ligand to metal Sensitive to solvent LMCT l High oxidation state metal ion l Lone pair ligand donor MLCT l Low lying pi, aromatic l Low oxidation state metal High d orbital energy

8-28

Solvent effect

8-29

Methods
Titration l Change of absorbance with solution variation pH, ligand, metal Photoacoustic effect l Emission of sound

8-30