PROCESS INSTRUMENTS

®
WESTERN RESEARCH
How AMETEK’s Western Research® Model
4000 Photometric Analyzer Works
In photometric analyses, the interaction
of electro-magnetic radiation energy with Beer-Lambert Law
the component to be measured results
in a loss of radiation (light) intensity.
The AMETEK 4000 analyzer operates
primarily in the near ultraviolet and visible I I0
region of the electromagnetic spectrum
(200 to 700 nm) and extends into the
near infrared to about 1,100 nm. Based
on Planck’s Law (E=hv), the lower the A = -log T - log
I0 = abc
wavelength of radiation (the higher the I
frequency), the higher the energy of the P 298
For Gases A = abc x x
photon. PA 273 + T
Figure 2
As shown on figure 1, photoelectron
exponential function of pathlength and concentration.
energies in the UV and visible regions are at
To provide a function linear with pathlength and
levels corresponding to energy transitions of
concentration, the nondimensional absorbance
valence electrons. In general, these transitions
(A) is defined on the figure; “a” is the
molar extinction coefficient and is
Vibrational and constant for a given compound at a
Valence Electron Rotational Energy
Energy Transitions Transitions given wavelength and within a given
matrix (liquid, solid, or gas), “b” is the
pathlength in centimeters, and “c” is
Ultraviolet Visible Infrared
the concentration in moles per liter.
100 nm 100 nm 800 nm 4 x 105 nm
(0.1 µm) (0.1 µm) (0.8 µm) (0.1 µm) A laboratory photometer or
spectrophotometer usually has
Wavelength a broadly emitting source such a
Figure 1
hydrogen discharge or tungsten lamp
(figure 3). The wavelength usually is
are broader and not as common as the rotational
isolated by a prism, grating, or interference filters.
and vibrational patterns in the infrared region.
For good monochromaticity, narrow bandpasses are
With the relatively high photoelectron energy
required. Consequently, light intensity is very low,
associated with the UV/visible region,
metallic discharge lamps with intense
line emissions and long life can be used
as light sources. Photodiodes, which
Classic Photometer
are sensitive, highly stable, and exhibit
very low noise, temperature coefficients,
and fatigue characteristic, are used as Detector Sample Filters or Source of
Monochromator Radiant Energy
detectors.
Beer’s Law shows the quantitative
way the loss of light intensity varies with
concentration and pathlength (figure
2). Basically, light intensity transmitted
Figure 3
through a windowed cell is an

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 WESTERN RESEARCH
and usually highly sensitive detectors such as Our experience has shown that most operators do
photomultipliers must be used. Photomultipliers have not like to use calibration curves, particularly if highly
high temperature coefficients and fatigue, and require nonlinear. They like to have a direct readout, and will
well stabilized high voltage power supplies. Light use the instrument more readily if the output is linear
from the monochromater passes through a window with concentration of the component measured.
cell (a cuvette) before striking the detector. zx Fast response is needed particularly for good
process control. Analyzer response usually is
Design Criteria For Photometric Analyzers
adequate; however, sample lag, the time it takes
Early in the development of process stream analyzers, the sample being extracted from the process to
it was realized that one could not take a laboratory reach the analyzer, most often limits response
instrument and put it in the field. You had a laboratory time. A fast “slip” stream with a high sample flow
instrument sitting in a hostile environment for which bypassing the sample cell often is used to increase
it was not designed. Over the years, a design criteria speed of response. In monitoring and/or controlling
philosophy was developed. Among these are: film thickness, a millisecond response often is
zx Ruggedness required because of the high speed at which the
zx Serviceability film is being produced.
zx Accuracy, Reproducibility, Stability From experience we have found that operators
zx Linear Readout retain a great deal more confidence in an
zx Fast Response instrument which can easily be checked for
response and calibration with a minimum of effort.
zx Ease of Calibration
zx Simplified Sampling Requirements zx Last, but not least, is a simple sample system.
Those who have been in the field for a long time
zx The instrument must be rugged; that is, very well
have found that sampling problems account
built. It is installed in a very hostile environment,
for some 80 to 90 percent of the problems in a
often with high vibration, and is not treated with
process stream analyzer installation. A design
tender loving care one so often finds in the
minimizing the need for extensive sample
laboratory. Associated with ruggedness is the
conditioning to the analyzer minimizes down time
need to meet the electrical classification of the
and gives higher reliability.
area in which it is installed.
zx The instrument must be readily maintained. It is Functional Diagram of Split Beam Photometric
designed so that parts are easily accessible and Analyzer
is not too complicated. The technician taking care
The AMETEK 4000 photometric analyzer (figure 4)
of it then will have a very positive feeling toward it,
was designed after an evolution of a large number
and the unit will be maintained.
of photometric analyzers extending from about 1942
zx Stability and reproducibility of a process
stream analyzer often must well exceed
that of a laboratory instrument. Since Split Beam Photometric Analyzer
analyzers often are discharged to the
atmosphere, accuracy often is limited in Optical
Sample
Beam Cell
the gas phase measurement because of Filter Splitter
variations in absolute pressure. Unless an Lamp
absolute pressure control is used, these Measuring
Photodiode
variations can amount to ±2 percent,
often adequate for most monitoring
applications. Reproducibility must be
Optical
high, particularly for good process control Filter
when the analyzer is often integrated
in a control loop. Stability in a plant
installation, where temperatures can vary Reference
Photodiode
greatly and voltage fluctuations and
vibrations can occur, must be such that Figure 4
the instrument provides reliable readings
day in and day out.
 WESTERN RESEARCH
- the design still is evolving. The split
beam configuration is shown here, and,
as seen later, meets many of the criteria
listed earlier. Light from the source,
usually a metallic lamp discharge with
discrete lines of emission, passes
through the windowed sample cell,
usually with quartz windows to provide
good ultraviolet light transmission.
Light transmitted through a cell is split
into two channels by a beam splitter, a
quartz plate coated with Inconel. The
transmitted portion of light passes
through a filter bundle which isolates the
one wavelength where the component to
Figure 5
be measured absorbs strongly, so that
light of this wavelength is the only light nickelous sulfate solution, a glass filter, and nickelous
striking the photodiode. The photodiode produces sulfate crystal sealed between two quartz discs, again
a current precisely proportional to the intensity of all used for blocking wavelengths. The next element
light striking it. Photodiode current is then fed to is a beam splitter, and the last is an interference filter,
a logarithmic amplifier, converting the current to a which has become very common. Interference filters
voltage varying as the logarithm of the current and, have blocking built in; but for ultimate isolation of
in turn, as the intensity of light at the measuring a specific wavelength, external blockers are often
wavelength. This logarithmic conversion linearizes added to improve linearity over wide absorbance
the Beer’s Law characteristic described previously. ranges. Incidentally, thin film coating technology
The reference channel is functionally identical to has been greatly extended in the past 30 years, and
the measuring channel in that it has a similar filter interference filters with excellent band pass and
bundle, photodiode, and amplifiers. However, this blocking characteristics now can be purchased fairly
filter bundle isolates a different wavelength, one where reasonably.
the material measured does not absorb or absorbs Figure 6 shows some of the light sources used.
very weakly compared to that of the measuring From left to right; an ST49 UV lamp is the most
wavelength. The amplifier outputs are subtracted commonly used. It is a medium pressure mercury
from one another, providing the logarithm of light discharge lamp used to produce a large variety of
intensities at the two wavelengths. This
differential signal is fed to the controller where
the instrument is electronically zeroed and
spanned. The controller output is then signal
fed to the recorder and/or process controller.
The advantage of the split beam configuration
is derived from looking at two different
wavelengths simultaneously. The instrument
inherently has the means of compensating for
particles or bubbles passing through the cell,
or light fluctuations which affect the intensity
of light at both wavelengths equally and tend
to be canceled out.
Figure 5 shows some of the optical
components used in this system. On the left
is a 2-cm thick quartz bottle with chlorine
used to block out wavelengths where chlorine
absorbs (300 to 375 nm). Clockwise from the Figure 6
chlorine bottle there is a quartz bottle with a
How AMETEK’s Western Research® Model 4000 Photometric
Analyzer Works

WESTERN RESEARCH
lines for monitoring in the UV region. The
next lamp is made by UV Products and
provides the 228-nm cadmium discharge
line in several applications. The third is
a low pressure mercury discharge lamp,
a Penray lamp used primarily for the
mercury resonance line at 253.7 nm. The
last is a rugged tungsten lamp used to
provide the light for color and near infrared
measurements.
Figure 7 shows how a line emitted by a
metallic discharge lamp can be isolated
Figure 7
readily to provide highly monochromatic
light without a monochromater. The
advantage of using metallic discharge To summarize split beam design advantages :
lamps is that the discharge lines are often zx There is internal compensation for particulate
several orders of magnitude in intensity above matter and bubbles in the sample stream.
background light, and very narrow. We cannot
zx There is internal compensation for dirty windows.
even talk in terms of half-bandwidth. Discharge
lines have one-tenth bandwidths less than zx There is internal compensation for variations of
0.1 angstrom. Furthermore, wavelengths are light intensity.
fixed and unchanging. Based on energy levels zx No moving parts increases reliability.
available for a valence electron to move, which
zx Modular design (figure 8) is highly flexible and
are fixed regardless of temperature, etc, the
allows for analyzing high temperature and high
light wavelength emitted results from the fixed
pressure samples without potential damage to
difference in valence electron energy levels.
electronics or optics.

Model 4000 Photometric Analyzer

Photometer Housing Sample Housing Lamp Housing

Figure 8

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4000 How it Works (06/13/07) Tel: 65 6484 2388, Fax: 65 6481 6588
One of a family of innovative process analyzer solutions from AMETEK Process Instruments.
Specifications subject to change without notice.