UltravioletVisibleSpectroscopy

IntroductiontoUVVisible
Absorptionspectroscopyfrom160nmto780nm
Measurementoftransmittance
Conversiontoabsorbance
* A=logT=bc

Measurementoftransmittanceandabsorbance
Beerslaw
Noise
Instrumentation

81

Measurement
Scatteringoflight
Refractionatinterfaces
Scatterinsolution
Largemolecules
Airbubbles
Normalizedbycomparisontoreferencecell
Containsonlysolvent
Measurementfortransmittanceis
comparedtoresultsfromreferencecell
82

BeersLaw
Basedonabsorptionoflightbya
sample
dPx/Px=dS/S
dS/S=ratioofabsorbancearea P
n
dP
adn
x
tototalarea

Px
S
* Proportionaltonumberof
P
0
absorbingparticles
Po an
ln
dS=adn
P
S
an
* aisaconstant,dnisnumber Po
log
ofparticles
P 2.303S
nistotalnumberofparticles
withinasample
o

83

BeersLaw
AreaScanbedescribedbyvolumeandlength
S=V/b(cm2)
Po
anb
log
SubstituteforS
P 2.303V
n/V=concentration
Substituteconcentrationandcollect
constantintosingleterm
Beerslawcanbeappliedtomixtures
Atot=Ax
84

BeersLawLimitations
Equilibriumshift
pHindicators
Needtoconsider
speciation
Weakacid
equilibrium

85

BeersLawLimitation
PolychromaticLight
Morethanone
wavelength

86

Noise

Limitedreadoutresolution
Darkcurrentandelectronicnoise
Photondetectorshotnoise
Cellpositionuncertainty
Changingsamples
Flicker

87

Instrumentation
Lightsource
Deuteriumandhydrogenlamps
Wfilamentlamp
Xearclamps
Samplecontainers
Cuvettes
Plastic
Glass
Quartz

88

Spectrometers

89

Spectrometer

Timeseparateddoublebeam
810

Spectrometer

Dipprobe

Multichannelphotodiodearray
811

ApplicationofUVVisibleSpectroscopy
Identificationofinorganicandorganicspecies
Widelyusedmethod
Magnitudeofmolarabsorptivities
Absorbingspecies
methods

812

MolarAbsorptivties
Rangefrom0to1E5
=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
813

Absorbingspecies
Electronictransitions
and n electrons
d and f electrons
Charge transfer reactions
and n (non-bonding) electrons

814

SigmaandPiorbitals

815

Electrontransitions

816

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
817

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

818

Solventeffects

819

Transitions
dd
3dand4d1stand2ndtransitionsseries
Broadtransitions
Impactedbysolution

820

Transitions

821

Dtransitions
Partiallyoccupieddorbitals
Transitionsfromlowertohigherenergy
levels
Splittingoflevelsduetospatial
distribution
similar

Axialdirection
822

Dtransitions
Bindingligandsonaxishavegreatereffecton
axialorbitals

823

Dtransitions
value dependent upon ligand field strength
<Br<Cl<F<OH<C2O42~H2O<SCN
<NH3<en<NO2<CN
increases with increasing field strength
ff
4fand5f(lanthanidesandactinides)
Sharpertransitions

824

Actinidetransitions
5
6+

Pu (835 nm)
4+

Absorbance

Pu (489 nm)
Normal
Heavy
Light

0
400

500

600

700

800

Wavelength (nm)

Figure2:UVvisspectraoforganicphasesfor13M
HNO3system

825

ChargetransferTransitions
Electrondonorandacceptorcharacteristics
Absorptioninvolvesetransitionsfrom
donortoacceptor
SCNtoFe(III)
* Fe(II)andneutralSCN
Metalisacceptor
Reducedmetalscanbeexception

826

ElectronicSpectra

Cr(NH3)63+
d3
Weaklowenergytransition
Spinforbidden
2strongertransitions
Spinallowed
* t2gandeg
transitions
Lower
energyto
higher
energy
CTathigherenergy
Ligandtometal
transition

827

Chargetransferbands

Highenergyabsorbance
Energygreaterthandd
transition
Electronmovesbetween
orbitals
* Metaltoligand
* Ligandtometal
Sensitivetosolvent
LMCT
Highoxidationstatemetalion
Lonepairliganddonor
MLCT
Lowlyingpi,aromatic
Lowoxidationstatemetal
Highdorbitalenergy

828

Solventeffect

829

Methods
Titration
Changeofabsorbancewithsolution
variation
pH,ligand,metal
Photoacousticeffect
Emissionofsound

830