Ultraviolet and VisibleAnalyzers

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Configurations: A. Photometers are nondispersive analyzers in which the source

radiates over its full ultraviolet (UV) spectrum, and discrete
wavelengths are separated by narrow (2 to 10 nm) bandpass filters.
Most process analyzers are nondispersive.
B. Spectrophotometers are dispersive analyzers in which a prism is
used to separate the spectral components of the UV spectrum.
Most laboratory analyzers are dispersive.

Types of Designs: Optics can be configured as single-beam, split-beam, dual-beam, or

flicker photom- eters. The process stream can pass through a
measurement chamber, or probe-type analyzers can be inserted into
the process stream using a retroreflector configuration. Most detectors
are capable of measuring the intensity of one wavelength at a time,
whereas photodiode arrays can detect all wavelengths simultaneously.

SELECTION CRITERIA:

Type of Sample: Gas, vapor, and liquid

Design Pressure: Normally atmospheric but it can also be pressurized up to 150 PSIG
(10.7 barg) to enhance sensitivity when analyzing gas samples. The
fiber-optic, diode-array type of in-line analyzer can operate at up to
730 PSIG (50 barg).

Sample Temperature: Standard units operate from 32 to 302 F (0 to 150 C); stack gas
analyzer can operate at up to 800 F (427 C).
Materials of Construction: Quartz and sapphire windows; other parts available in stainless
steel, Hastelloy®, Monel®, titanium, Teflon®, Kynar®, and all other
conventional materials

Wavelength Ranges: Standard ranges include 200 to 800 nm or 400 to 1100 nm.

Cell Lengths: Standard units are from 0.039 to 39.4 in. (1 to 1000 mm); for
fiber-optic diode-array analyzer, 0.3 to 10 mm.

Inaccuracy: 2% of full scale for most; 1% of full scale for the fiber-optic
diode-array type of UV-visible analyzer
UV Absorption
Fewer compounds absorb in the UV region than in the IR region, and the UV absorption pattern of a compound
is not as distinctive as is its IR “fingerprint.” On the other hand, UV analyzers provide better selectivity in
applications in which the sample contains air and humidity, because these materials do not absorb in the UV region.

UV analyzers are also more sensitive than IR detectors. Figure 8.61a shows the absorbance of sulfur and
nitrogen dioxides in the UV region. On an equal path-length basis, the UV absorbance of liquids is stronger than
that of vapors in proportion to their densities.

THEORETICAL ASPECTS

Ultraviolet, visible, and near-infrared photometers and spec- trophotometers are widely used in the process
industries. On-line UV analyzers have been used since the 1940s.

The Radiation Spectrum

The ultraviolet (UV), visible (VIS), and infrared (IR) regions of the electromagnetic radiation spectrum are
shown in Figure 8.61b. The UV region covers the wavelengths from 200 to 400 nm. The visible region extends
from 400 to 800 nm, and the near IR (NIR) region covers from 0.8 to 2.50 m. Nanometer units are commonly
used in the UV/VIS region, and micrometers (or microns) are normally used in the NIR region (Table 8.61c).
The UV-VIS-NIR is a relatively

shorter the wavelength (the higher the frequency) the more penetrating the radiation becomes.
Compounds absorb at various frequencies of radiation depending on the energy of their molecular transitions.
High- energy electronic transitions are observed in the shorter- wavelength UV-VIS regions. Moderate-energy
(vibrational and rotational) transitions are observed in the longer-wave- length IR region.
 Electromagnetic radiation spectrum from the audible
frequency up to that of the cosmic rays.

The Beer–Lambert Law

Absorption spectroscopy is the measurement of radiation intensity at spectral wavelengths that are characteristic of
the compound being monitored. When radiation enters a process sample, only part of the light is
transmitted. The remainder of the radiation is absorbed or reflected, depending on the concentration of the sample
and on the wavelength being measured. If particles are present in the sample, part of the radiation will be
scattered. The Beer–Lambert law is the fundamental law that gov- erns quantitative analysis by absorption
spectroscopy.

The Beer–Lambert law is the fundamental law that gov- erns quantitative analysis by absorption spectroscopy. This
law states:
A abc
where
A absorbance
a molar absorptivity
 b sample path length
c concentration of absorbing species

The absorbance of a sample is measured indirectly by measuring the transmitted radiation. The
relationship between absorbance and transmittance is

W he r e : T = t r a n s mi t t a n ce

Absorption of light.

Calibration Calibration methods for photometers involve the measurement of absorbance for several
concentrations of the component being measured. When a plot of absorbances vs. concentration gives a
linear response, the method obeys the Beer–Lambert law. When the photometer exhibits a nonlinear
response, a linearizer circuit is used to compensate for the nonlinearity.

Applications UV photometers are normally used for the measurement of a key single component in a process
stream. The following applications are examples of typical UV photometer measurements: 1. Residual
chlorine in water in pulp and paper process 2. Total aromatics in wastewater 3. Chlorine in dichloroethane in
vinyl chloride processes 4. Hydrogen sulfide and sulfur dioxide in the Claus sulfur recovery process in the
petroleum refining industry 5. Sulfur dioxide in incinerator stack emissions
 Block diagram showing the main components of a spectrophotometer.

How the UV source is used in an open-path spectrometer

Readouts:
Analog meters, digital meters, strip chart recorders, and video display tubes (VDTs) are examples of
readout devices used in photometers and spectrophotometers. On-line photometers are usually microprocessor
operated and usually have both a 4 to 20 mA analog output and a digital output, which is sent to the process control
computer. Spectrophotometers can incorporate a strip chart recorder to record a spectrum of the analyzed sample.
The spectrum is a plot of percentage transmission or absorbance readings as a function of wavelength.
UV ANALYZER DESIGNS

The proven industrial designs used for process UV analyzers include the following:

1. Single-beam

2. Split-beam

3. Dual-beam, single-detector

4. Dual-beam, dual-detector

5. Flicker photometer

6. Photodiode

7. Retroreflector

CONCLUSIONS

The packaging of ultraviolet and visible analyzers usually separates the amplifier/controller from the optical system.
Some designs provide complete housing separation of the sample cell to isolate the electrical components from
the flowing sample. The sample cell can then be temperature controlled when necessary, independent of the
remaining optical system.
Vapor bubbles cannot be tolerated in the sample, because they will generate noise in the optical reading. If
a gas sample pressurized cell is used, the cell pressure must be kept constant.
The UV analyzer has the unique and convenient feature that it offers a simple means of checking the
calibration by use of a selected interference or broadband fi . Once the calibration (using known samples) is
completed, a fi that absorbs at the wavelengths of interest can be used thereafter.