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Introduction
A.) Absorption: electromagnetic (light) energy is transferred to atoms, ions, or molecules
in the sample. Results in a transition to a higher energy state.
E1
(excited state)
Eo
(ground state)
Power (P): energy of a beam that reaches a given area per second
B.) Terms:
1.) Beers Law:
A = bc
The amount of light absorbed (A) by a sample is dependent on the path length (b),
concentration of the sample (c) and a proportionality constant ( molar absorptivity)
B.) Terms:
1.) Beers Law:
A = bc
%Transmittance = %T = 100T
Selector
Creates Proper
Narrow Band pass:
Stable:
Selects Desired
Constant P
Large Light Throughput:
Good Precision
Increase P
Intense:
Increase P
Easier to See Absorbance
Detector
Stable
Sensitive to of Interest
D2 or H2 Gas
Filament
40V
Electric Arc
Tungsten Filament
Temperature Dependence of
- cost ~ $10-15
- problems: higher heat, more stray light, higher cost, shorter lifetimes
b) Wavelength Selectors:
1. Monochromator
- separates frequencies () from polychromatic light.
- allows only certain s to be selected and used.
i.) Dispersing Monochromator:
a) Prism: based on refraction of light and fact that different s
have different values of refraction index (i) in a medium.
1sin1sin2
n = d(sin i + sin r)
n = d(sin i + sin r)
Example 5: A monochromator was equipped with an echellete grating of 2500 blazes per
millimeter, where 2.0 cm of the grating was illuminated. At approximately 430 nm, what
minimum wavelength difference could in theory be completely resolved by the instrument?
Important Components:
i) Entrance slit
ii) Collimating lens or mirror makes radiation parallel before hitting
dispersing element
iii) Grating or Prism
iv) Focusing Lens or mirror to focus light of desired on exit slit.
Important Components:
i) Entrance slit
ii) Collimating lens or mirror makes radiation parallel before hitting
dispersing element
iii) Grating or Prism
iv) Focusing Lens or mirror to focus light of desired on exit slit.
Grating
Prism
Type of Dispersion
Size
Stray Light
smaller
larger
Less of problem
range of
use
unlimited
Limited
( 350 nm)
at
a) Filter: Monochromators
1) Absorption Filters
- material remove undesired s by absorbing them.
- typically made from colored glass or dye
suspended in gelatin between glass plates.
- fixed , much energy lost due to absorption.
- cheap
2) Interference Filters
- made up of thin layers of metal and dielectric (eq. CaF2)
material sandwiched between glass plates
- dielectric material is of uniform, known thickness.
- metal acts as partial mirror
2) Interference Filters
As light enters, some goes through but some is
reflected. The distance the light travels before it
exits generates constructive and destructive
interference on the other side of the filter.
s transmitted through filter:
N = 2d
refractive index
d thickness of dielectric
N integer
- wavelength
Band pass can be 1-20nm. (narrow), but filter is fixed at given value as much intensity
is lost due to reflection
vii.) Detectors:
a) earliest detectors were the eye or film.
now use devices that convert light to electrical signal
b) for good detector want:
high sensitivity
good signal to noise ratio
constant response over range of interest
signal light intensity
fast response
little or no signal in absence of light (dark current)
Process:
light of sufficiently high energy passes through the thin transparent silver layer and
hits selenium causing electrons to be released which move across barrier toward
silver layer (electropositive) and collected at iron layer to neutralize selenium layer.
-
Advantage: cheap, rugged, no external power source, good for portable instruments.
Disadvantage: not very sensitive, shows fatigue (decrease in response with continued
illumination), difficult to amplify signal-small resistance (Ohms law: I=(V/R)).
2) Vacuum Phototube
(Photoemission material)
Process:
- photoemission material (Cs2O) ejects an e- when hit with a photon
(photoelectric effect).
- potential of 90V across cathode(-) and anode(+). As light hits cathode, eare emitted from cathode and attracted to anode. Produces current that can be
measured.
- current number of photons.
- smaller current then photovoltaic cell, but can be amplified because of larger
resistance.
- 90V difference sufficient to collect all e- produced (working at saturation).
- various photoemission material (sensitive to certain photon s)
2) Vacuum Phototube
Process (cont.):
- various photoemission material (sensitive to certain photon s)
Process:
a) light hits cathode and e- emitted.
b) an emitted e- is attracted to electrode #1
(dynode 1), which is 90V more positive.
Causes several more e- to be emitted.
c) these e- are attracted to dynode 2, which is
90V more positive then dynode 1, emitting
more e-.
d) process continues until e- are collected at
anode after amplification at 9 dynodes.
e) overall voltage between anode and cathode
is 900V.
6
f) one
photon produces
107 electrons.
Advantages: very sensitive to low
intensity,
very fast10
response.
g) current
is supply,
amplified
and measured
Disadvantages: need high voltage
power
intense
light damages
- Light shining on the silicon diode provides the energy needed for the
electrons to travel into the P region.
- Flow of current is related to intensity of light.
A vidicon tube contains many silicon diodes each insulated from each
other (~ 8m apart). The e- gun or light source sweeps the P-region
and charges the diodes. (Television)
Schematic of Spectronic 20
Spectronic 20
Selector mirror or beam chopper: mirrors which rotate at 60 cps, reflecting the light
alternatively to the reference and sample cells
All light is combined and goes to a single PMT. Output of PMT is 60 cps square wave. Po and
P are measured alternatively at a rate of 60 times per second.
Advantages: scanning, little drift only one PMT.
Disadvantages: more complex and expensive