Topic 1 Part 2

Basic components of
spectroscopic instrumentation

Principles of the spectroscopic method

Optical spectroscopic methods are based upon following

phenomena:
absorption
Fluorescence
Phosphorescence
Scattering
emission and
chemiluminescence
The basic components needed for measuring each
phenomenon are remarkably similar although they differ in
some configurations and they are applied in different regions
of the electromagnetic spectrum (ultraviolet, visible, or
infrared).

Typical spectroscopic instruments contain five components including;

Sources (UV and visible)

Wavelength selector
Sample containers
Detector
Signal processor and readout

(1)

(2)

Source
lamp

Wavelength
selector

hv

hv

(3)

(4)

(5)

(6)

Sample
holder

Wavelength
selector

Photoelectric
transducer

Signal
processor
and
readabout

hv

hv

Basic components of various types of instruments for optical spectroscopy

(hv = photon, I = information data)

i.

A stable source of radiant energy

A source must generate a beam of radiation with sufficient
power for relatively easy detection / measurement.
Stable source results in a stable output.
There are two types of source radiation:
1. Continuum source

2.

This emits continuous bands of electromagnetic

radiation over relatively large wavelength regions.
Line source
This emits a limited number of lines or bands of
electromagnetic radiation over relatively limited
ranges of wavelength.

Continuous sources

Provides a broad range of

lights wavelengths
Usually not very strong
Do not have a uniform
intensity through out their
emission spectra.
A wavelength selector must
be used if one wants to use
a specific wavelength.

Line sources

Provides very specific

wavelengths of light.
Usually very strong
Very high intensity.
E.g. Metal vapour lamp

Mercury vapour lamp

generates high intensity light at

254 nm.
Cadmium lamp

generates light at 225 nm

Zinc lamp

generates light at 214 nm.

None of the lamps emits strictly
monochromatic light
Light of other wavelengths present
If monochromatic source of light is
required, an appropriate filter would
be needed.

Wavelength, nm

100

200

Spectral region

VAC

(a) Sources

Ar lamp

400
UV

700

Visible

2000

Near IR

20000
IR

Xe lamp

Continuum

H2 or D2 lamp
Tungsten lamp

source

Nernst glower (ZrO2 + Y2O3)

Hollow Cathode lamps

Line
source
(b) Detector

Lasers

Wavelength,
Photographic plate
nm
Photomultiplier tube
Phototube
Photocell
Silicon diode
Charge transfer detector
Photoconductor

ii.

Sample cells
These are containers for holding a
sample (solid, liquid or gas) which are
transparent to all wavelengths ()
There are three areas of interest:
1.
UV:

2.

Visible:

3.

quartz (200-3000 nm)

fused silica (150-3000 nm)
glass (375-2000 nm)
Quartz
fused silica
plastic (380-800 nm)

IR:

KBr (100-40,000 nm)

NaCl crystals (200-18,000 nm)

iii.

Devices that attempt to select the single wavelength () of electromagnetic radiation which
will reach the detector at any given time.
The output is related to sensitivity, selectivity, and linearity of the calibration plots.
1.
Ideal output:
2.
3.

Wavelength selectors

Electromagnetic radiation of a single wavelength/frequency

Real output:
Limited, narrow, continuous band of wavelengths
Effective bandwidth:
A narrower bandwidth representing better performance.

Types of wavelength selector:

Wavelength Selectors for Spectroscopy

Type
Continuously Variable

Wavelength Range, nm

Grating monochromator

100 40000

Prism monochromator

120 30000

Discontinuous
Interference filter
Absorption filter

200 14000
380 750

Note

3000 lines/nm for vacuum UV;

50 lines/nm for far IR

Wavelength selector (monochromator)

All monochromators contain;

An entrance slit

A collimating lens

A dispersing device (prism / grating)

A focusing lens

An exit slit
Polychromatic radiation enters the
monochromator through the entrance slit.
The beam is collimated, and then strikes
the dispersing element at an angle.
The beam is split into its component
wavelengths by the grating or prism.
By moving the dispersing element or the
exit slit, radiation of only a particular
wavelength leaves the monochromator
through the exit slit.

Bunsen prism monochromator

Prisms can be used to disperse ultraviolet, visible, and
infrared radiation.

Czerny-Terny Monochromator

Wavelength Selection, Scanning Monochromator

Wavelength selector (filter)

It is often important to use optical

filters in addition to
monochromators.
Optical filters are used to
compensate for the less-than-ideal
behavior of monochromators.
Two types of filter available:
1.
Colored-glass filters.
2.
Thin film filters
Function and advantages:

Maximise the instrument sensitivity

by;
rejecting possible interfering
wavelengths
eliminating the scattered light, stray
light, or sample impurities.
Transmit or reject laser lines

Almost any desired

transmission curve can be
obtained by careful
selection of the filter used
in addition to the
monochromators

Fig: Rejection of scattered

light from the 0.8-M
tryptophan, solution using a
bandpass filter (top) or a
polarizer but no bandpass
filter (bottom). The emission
polarizer was oriented
vertically (||) or horizontally
().

iv. Radiant detector

A device that converts the wavelength, (energy) to the electrical

signals, and will produce a readout representing the signal value.
i.e. a detector takes the light that pass through the sample and
converts into a signal that is easily measured.
The most common detector is the photomultiplier tube (PMT)
The PMT consists of
photoemissive cathode
a cathode which emits electrons when struck by photons of
radiation
several dynodes
which emit several electrons for each electron striking them
anode

Photomultiplier Tube (PMT)

A photomultiplier tube (PMT)

uses a cascading effect to
produce 106 to 107 electrons
for each photon that hits the
detector.
At first the photon hits a
photoemissive cathode that
releases electrons.
The higher the intensity the
more electrons are released.
These electrons then go on
hitting a series of cathodes
that continues to release
more electrons
Finally the quantity of
electrons is measured by the
anode producing a signal.

Schematic of PMT

v.

Signal processor and readout.

Signal processor is ordinarily an electronic device
that amplifies the electrical signal from the
transducer
Readout devices display the transduced signal on;

a meter scale
an oscilloscope face
a digital meter
a recorder chart
the scales of potentiometer
cathode ray tubes, i.e., monitors