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QCanalytic 1
QCanalytic 1
Spectrophotometric Methods
2007
By the end of this part of the course, you should be able to:
If you have difficulty to understand above topics, find extra reading materials!
Or discuss with me after the lecture.
c/n= nl
Therefore:
Energy is inversely proportional to wavelength
but proportional to wavenumber
Frequency Scanning Techniques: a few definitions
Emission method: source of light is sample
Absorption method: intensities of a source with and without the sample in place are
compared
In quantitative analysis:
common to work at 1 wavelength
running a spectrum is an important initial step (to select best conditions)
Regions of Electromagnetic Spectrum-the “colour” of light
Fig. 18-2
Electronic structures of simple molecule
Energy
Excited state
Singlet
S1
Vibration states
T1 Excited state
Triplet
D
Dissociated states
S0 Bond length
Ground state
Interaction between photon and molecule
S0 S1 transition
S1
T1
S1
T1
UV-vis
D
A F
P
S0
IR
S0
Key concept from energy diagram
Electronic structures
Internal conversion
Intersystem crossing
Luminescence-fluorescence/phosphorescence
Type of optical spectroscopy
UV-vis absorption spectroscopy (UV-Vis)
FT-IR absorption/transmission spectroscopy (FTIR)
Atomic absorption spectroscopy (AAS)
Atomic fluorescence spectroscopy (AFS)
X-ray fluorescence spectroscopy (XFS)
Monochromator design
Instrument principle
Quantitative methods
Optical spectrophotometer components
Excitation sources
(a)
(c)
(b)
Fig. 13-12, pg. 315 "Instrument designs for photometers and spectrophotometers”
Light sources Brightness
Line width
What is the important properties of a source? Background
Black-body radiation for vis and IR but not UV Stability
- a tungsten lamp is an excellent source of black-body radiation Lifetime
- operates at 3000 K
- produces l from 320 to 2500 nm ( How much in cm-1, J, Hz and eV?)
For UV:
- a common lamp is a deuterium arc lamp
- electric discharge causes D2 to dissociate and emit UV radiation (160 – 325 nm)
- other good sources are:
Xe (250 – 1000 nm)
Hg (280 – 1400 nm)
Lasers:
- high power
- very good for studying reactions
- narrow line width
- coherence
- can fine-tune the desired wavelength (but choice of wavelength is limited)
- £££ expensive £££
Sample a source containers:
for UV: quartz (won’t block out the light)
for vis: glass [l 800nm (red) to l 400 nm (violet)]
for IR: NaCl (to or 15384 nm or 650 cm-1)
KBr (to 22222 nm or 450 cm-1)
CsI (to 50000 nm or 200 cm-1)
Criteria
High transmission
Chemically inert
Mechanically strong
Monochromators
Early spectrophotometers used prisms
- quartz for UV
- glass for vis and IR Why?
http://www.mrfiber.com/images/
cddiffract.jpg
10mmx10mm
http://www.veeco.com/library/nanotheater_detail.php?type=
application&id=331&app_id=34
Monochromators: cont’d
What is the purpose of concave mirrors?
Polychromatic radiation enters
The light is collimated the first concave mirror
Reflection grating diffracts different
wavelengths at different angles
http://oco.jpl.nasa.gov/images/grating_spec-br.jpg
Interference in diffraction
d sin(q)+d sin(f)=nl
d
Bragg condition
q>0
Phase relationship
f
f<0 q n=1, 2, 3 In-phase
n=1/2, 3/2, 5/2 out-phase
Monochromators: reflection grating
Monochromators: reflection grating
Each wavelength is diffracted off the grating at a different angle
Groove dimensions and spacings are on the order of the wavelength in question
In order for the emerging light to be of any use, the emerging light beams must be in phase
with each other
Angular resolution:
As: d sin(q)+d sin(f)=nl
So: n Dl=d cos(f) Df
Therefore: Df/Dl=n/[d cos(f)]
What does this mean?
Monochromators: slit
Bottom line:
- it is usually possible to arrange slits and
mirrors so that the first order (n = 1) reflection
is separated
- a waveband of ca. 0.2 nm is obtainable
A diode is a pn junction:
under forward bias, current flows from
n-Si to p-Si
under reverse bias, no current flows
boundary is called a depletion layer or
region
Photodiode Array
- Electrons excited by light partially discharge the condenser
- Current which is necessary to restore the charge can be detected
- The more radiation that strikes, the less charge remains
- Less sensitive than photomultipliers several placed on placed on single crystal
- Different wavelengths can be directed to different diodes
- Good for 500 to 1100 nm
- For some crystals (i.e. HgCdTe) the response time is about 50 ns
No moving parts!
Simple mechanical and optical design, very compact.
Photodiode Array Spectrophotometers
vs Dispersive Spectrophotometers
Dispersive Spectrophotometer:
- only a narrow band of wavelengths reaches the detector at a time
- slow spectral acquisition (ca. 1 min)
- several moving parts (gratings, filters, mirrors, etc.)
- resolution: ca. 0.1 nm
- produces less stray light greater dynamic range for measuring high absorbance
- sensitive to stray light from outside sources i.e. room light
Photodiode Array
Spectrophotometer:
- no moving parts rugged
- faster spectral acquisition (ca.
1 sec)
- not dramatically affect by room
light
Fluorescence vs phosphorescence
Absorption vs emission
Why?
Fluorescence spectroscopy
Fluorescence spectroscopy
Light source Beam
splitter Q: why the emission is
measured at 90 relative to
Excitation
monochromator
sample the excitation?
Emission
Monochromator
Reference
diode
Emission spectrum: hold the excitation wavelength steady and measure the emission at
various wavelengths
Excitation spectrum: vary the excitation wavelength and vary the wavelength measured
for the emitted light
Fluorescence spectroscopy: well defined molecules
Summary of spectrophotometric techniques
• Describe the main components of a spectrophotometer and distinguish between
single double beam instruments
• Describe suitable sources for ultraviolet (UV)/visible (vis), infra red (IR) and atomic
absorption (AA) instruments
• Describe and assess advantages and disadvantages of various monochromators e.g.
Prism, diffraction gratings
• Explain how to asses the quality of grating
• Explain how photomultipliers and diode detectors work
• Explain the advantage of multiplex detecting
• Describe the luminescence spectroscopy and energy transfer process
• Compare the emission and absorption spectrum