Chapter 3

Spectroscopic Instrumentation
Types and components
 Compartments of the spectroscopic instrument:

All spectroscopic instruments contain six common components:

• Radiation source: Stable source of radiant energy

• Wavelength selector: for selecting a narrow band of λ’s from the source
• System of slits (entrance and exit): to narrow the wavelength band.
• Sample cell: transparent container for holding the sample
• Detector : for converting radiant energy into electrical energy
• Readout device: to read the response of the detector on a meter scale,
digital meter or a recorder chart
Radiation Source:
Source Wavelength Region
Ar lamp < 200 nm Vacuum UV
Xe arc lamp 250-600 nm UV-Vis
H2 and D2 discharge lamps 185– 375 nm UV
Tungsten lamp 350 – 2500 nm UV-Vis, NIR
Nernst glower (ZrO2 + V2O3) 400 – 20 000 nm Vis, IR
Nichrome wire 750 – 20 000 nm IR
(Ni + Cr)
Globar (SiC or rare earth oxide) 1200 – 10 000 nm IR
Laser Monochromatic UV-Vis, IR
light
what are the common source of
radiation for UV spectroscopy?
IR spectroscopy? Visible
spectroscopy?
UV radiation sources: H2 and D2 discharge lamps
❑ Most common UV source
❑ It has about three times the
spectral output of the H2 lamp
❑ Continuum from 190-400 nm,
with high output in the
ultraviolet
❑ high voltages (300 to 500 volts)
excite the molecular deuterium
contained within the bulb to a
higher energy state. The
deuterium then emits light as it
relaxed back to its initial state.
This continuous cycle is the origin
of the continuous UV radiation.
 Visible light source:
Tungsten, W, filament (Lamp):
Tungsten filament in a transparent envelope filled with a
mixture of inert gases such as N2 and Ar (the atmospheric
air is removed).
A small amount of halogen gas is added to prolong the
heater's operational life (How?!).
T : about 1100 K
λ : 350 – 2500 nm (0.35 – 2.5 μm)
Region : UV- vis - Near IR

G.R

The presence of the halogen gas with the filament produces a chemical reaction which
redeposits evaporated tungsten to the filament, increasing its life and allowing the
lamp to be operated at a higher temperature than a standard gas-filled lamp.
 IR radiation sources:
Nernst Glower:
Heated rare earth metal oxide rod Zirconium (IV) oxide (ZrO2), Yttrium Oxide (Y2O3) and
Erbium oxide (Er2O3) or Vanadium (III) Oxide (V2O3)
T : about 1500 K
λ : 1 – 50 μm
Region : mid to far IR

The Globar:
Heated silicon carbide (SiC)
rod.
T : about 1500 K
λ : 1 – 50 μm
Region : mid to far IR
 Wavelength selector:

A- Monochromators: B- Filters:
convert polychromatic radiation from the Remove some unwanted features from a
EMR source to monochromatic signal.
radiation.
1. Prism: 1. Absorption filter
2. Diffraction grating: 2. Interference filter

Prism Grating filters 7

 A- Monochromators: Idea: the incoming radiation
is refracted on both surfaces
1- Prisms: of the prism
Explanation:
Light changes speed as it moves from one medium to another. This change
causes the light to be refracted and to enter the new medium at a different
angle. The degree of bending of the light's path depends on the angle that
the incident beam, and on the ratio between the refractive indices of the two
media. This phenomenon is known as dispersion.
Shorter λ’s are refracted more than longer λ’s.

λ1 > λ2 8
Materials used to manufacture Prisms in UV, Vis and IR regions :
Monochromators for UV, Vis and IR regions are all the same. Only the materials from
which they are fabricated depend upon λ region of intended use.

Region Material
UV Quartz or fused Silica Transparent in the UV
region
Visible Glass Cheap and transparent
in the visible region
IR Alkali halides or alkaline earth Must kept dry WHY?!
halides: NaCl , KCl, KBr, LiF, CaF2,
AgCl, CsBr, CsI
 Dispersion and Resolving power:
The resolving power (R )
It is the ability of the
monochromator to separate
adjacent wavelengths of
radiation.
R = av λ / ∆λ
where, λ = average wavelength
used for the measurement
∆λ = difference between the
two wavelengths resolved
Dispersion (D )
It is the amount of separation in
space between wavelengths on
the focal plane. It is defined as the
distance x (mm) for each
nanometer (nm) of separation.
D=∆x/∆λ
where, ∆ x = the distance between
the two wavelengths
∆ λ = difference between the two
wavelengths dispersed
 Example 3.1
Determine the resolving power R of an instrument that is
capable of separating two adjacent peaks at 207.3 and
215.1 nm. If the two peaks are separated on the focal plane
of the instrument by 2.5 mm, calculate the dispersion D of
the instrument.
The answer:

av λ = (207.3 + 215.1)/2 = 211.2 nm

∆λ = 215.1 – 207.3 = 7.8 nm
R = 211.2 / 7.8 = 27 unitless
D = 2.5 mm / 7.8 nm = 0.32 mm/nm
 Example 3.2

What is the needed resolving power of a prism to prevent

any mutual interference between the following
wavelengths: 623, 633, 630, and 625 nm

The answer:

λ' δλ R
623 624 2
312
625
627.5 5
630 125.5
633 631.5 3
210.5
Minimum resolution power is ≥ 312
2- Gratings: Idea: It splits light into several beams travelling in
different directions. The directions of these beams
depend on the spacing of the grating and the
wavelength of the light
Explanation:
Grating consists of a large number of parallel lines (grooves) ruled on a highly
polished surface such as aluminium (about 15,000 – 30,000 per inch for UV-Vis
and 1500 – 2500 per inch for IR). The grooves act as reflecting centers for rays
falling on the grating. The result is equal dispersion of all λ’s of a given order.

14
The resolving power of the gratings depends on the number of
grooves and is better than that of a prism.

The grating equation is: n = d (sin i - sin  )

Where
d = distance between grooves,
i = angle of incidence
 = angle of defraction.
n = diffraction order
(it is an integer representing
the propagation-mode of interest)

Schematic diagram of
diffraction from a grating.
 Example 3.3

A reflective diffraction grating contains 1750 grooves per

mm. The angle of incident of a band of polychromatic
radiation was 48.2O. Calculate the wavelength that are
diffracted at the angle of 11.2O.

The distance between grooves d = 1 mm/1750 = 5.71 x 10-4 mm

= 571 nm
nλ= d (sin i - sin )
nλ= 571 (sin 48.2 - sin 11.2)
nλ= 314.76
For n =1 then λ= 314.76 nm
For n =2 then λ= 157 nm
For n =3 then λ= 105 nm
 Types of Gratings:
Master grating
• It consists of a hard,
optically flat, polished
surface upon which
grooves have been ruled
with a diamond tool.
• lower fabrication costs
Compare between the
Master and Holographic
gratings in the cost and
the tool to engrave the
patterns? Which is more
perfect and why?
Holographic grating:
• produced by exposing a
photoresist layer to a pair of
identical laser beams leaving
a grooved pattern that can
be coated with aluminium
• its cost is high,
• provides spectra free from
stray radiation and ghosts
(double image). (more perfect
compared to Master grating)
B- Filters:
Filters prevent the passage of radiation at all wavelengths
except in a fixed-wavelength region

1- Absorption Filters:

❑ Vis region
❑ They are made of glass and contain chemicals (dyes) that
absorb all unwanted radiation except that desired to pass.
They are less expensive. (could be used to solve the problem of
undesired luminescence substance that cause deviation from Beer’s law)
 2- Interference Filters:
❑ UV, Vis and IR regions
❑ It consists of two layers of glass on the inner surface of the
glass, a thin semitransparent film of metal is deposited. It has
an inner layer of transparent material such as quartz or calcium
fluoride CaF2.
❑ Radiation striking the filter exhibits destructive interference,
except for a narrow band for which the filter is designed to
transmit.

Schematic cross section of an interference filter.

Interference of adjacent waves that are a) 0o , b) 90o and c) 180oout of phase.

Schematic diagram to show the conditions for constructive interference

Sample container (Cells):
must be made of material that is transparent to radiation in
the special range of interest.
Region Material
UV Quartz or fused Silica
Visible Glass – Plastic
IR Alkali halides or alkaline earth
halides: NaCl , KCl, KBr, LiF, CaF2,
AgCl, CsBr, CsI
AgCl cells are often used for wet
samples or aqueous solutions. These
are soft and gradually darken due
to exposure to visible light
Transparent in the UV
region
Cheap and transparent in
the visible region
Must kept dry (stored in
desiccators ) to protect
them from the atmospheric
moisture.
They require periodic
polishing to remove
“fogging” due to moisture
contamination.
Quartz cell for UV spectrophotometer
Detectors (Transducers):

A transducer converts various types of chemical

and physical quantities into electrical signals such as
electrical charge, current, or voltage.

Type Wavelength range(nm)

Photon detectors
Phototubes (UV-Vis) 150 ~ 1,000
Photomultiplier tubes (UV-Vis) 150 ~ 1,000
Silicon diodes(UV-Vis) 350 ~ 1,100
Photoconductive cells (IR) 1,000 ~ 50,000
Type Wavelength range(nm)
Thermal detectors (IR)
Thermocouples 600 ~ 20,000
Bolometers 600 ~ 20,000
Pneumatic cells 600 ~ 40,000
Pyroelectric cells 1,000 ~ 20,000

What is the function of

transducers?
 1- Phototube (UV-Vis):

❑ It consists of a photoemissive cathode and an anode in an

evacuated transparent envelop.
❑ A high voltage is applied between the cathode and the anode
(90 V).
❑ When a photon strikes the cathode, an electron is emitted and
attracted to the anode (+), causing a current to flow that can be
amplified and measured. The number of electrons ejected from
the photoemissive surface is proportional to radiation that
strikes the cathode.
❑ Different phototubes are available for different regions of
the spectrum:
• High sensitive, made up of K, Cs and Sb.
• Cs-Sb cathode gives a device that is very sensitive in the
ultra-violet region.
• Cs on oxidized Silver gives a cathode that is most sensitive
to infra-red
2- Photomultiplier tube, PM (UV-Vis):

PM tube has advantage to measure low radiant power and

highly sensitive to UV-Vis radiation.
• The photocathode surface of PM is similar to phototube and
emits electrons when exposed to radiation.
• It contains 9 additional electrodes called dynodes.
• Dynode 1 is maintained 90 V from the cathode, and electrons are
accelerated toward it.
• Upon striking the dynode, each photoelectron causes emission of
additional electrons; these, in turn, are accelerated towards dynode
2, which is 90V more positive than dynode 1.
• Again, several electrons are emitted for each electron that strikes
the surface.
• This process is repeated 9 times;
• 106 - 109 electrons have been formed
for each incident photon.
• The electrons are collected finally
to the anode and then electronically
amplified and measured.
 3- Silicon diode (UV-Vis):
❑ Silicon diodes are more sensitive than vacuum phototube, but less sensitive than
photomultiplier.
❑ It is a semiconductor device that converts light into current.
❑ The current is generated when photons are absorbed in the diode.
❑ A silicondiode consists of 2 semiconductors (n-type and p-type) formed on a
silicon chip.
n-type : silicon – phosphorus
p-type : silicon - boron

If radiation is allowed to invade on the chip, holes (+) and electrons are formed in the
depletion layer which are swept through the device to produce a current that is
proportional to the radiant power.
4- Diode array (UV-Vis):
• Linear array of silicon diodes on one chip.
• It consists of hundreds of silicon photodiodes positioned side
by side on a single silicon crystal or chip (1024 diode
elements in a couple of cm).
• Each has an associated storage capacitor that collects and
integrates the photocurrent generated when photons strike the
photocathode.
• Diode array records an entire spectrum in a few (5-100 )
milliseconds.
 IR Detectors
• Thermocouple
It consists of two dissimilar metal wires e.g. antimony and
bismuth, connected at two points. When a temperature difference
exists between the two points, a potential difference is developed,
which can be measured. One of the junctions, is placed in the path
of the light from the monochromator.
response times of about 60 ms
 IR Detectors

• Thermopile
It consists of up to 6 thermocouples in series, mounted
in a vacuum to minimize heat loss by convection.
They have response times of about 30 ms.
 IR Detectors

• Bolometers and thermistors

Bolometer is a type of resistance thermometer constructed of strips of
metals as platinum or nickel or semiconductor (thermistors). Their
changes in resistance are measured in a Wheatstone bridge circuit.
Rapid response → 4ms. Which IR detector has the
fastest response to the
photons?
Give examples on IR
detectors? UV-vis
detectors? The Working
idea of each..?

What is the advantage of

Wheatstone bridge PM over the phototube?
 Problems on Chapter 3

1- Deduce which of the following elements will cause mutual interference in quantitative
analysis using a monochromator with resolving power (R) equals 300?

Element 
Mn 4033
K 4044
Pb 4058
Ga 4082

2. The needed resolving power of a prism of an instrument (R) to separate two adjacent
wavelengths at 5110 and 5120 nm is:
A) 0.5
B) 1.96 X 10-3
C) 5115
D) 511.5