This monograph presents an introduction to the current status and
future potential in the application of millimetre wavelength
spectrometry to the quantitative analysis of gaseous mixtures. It will
therefore be of interest for chemists and other people working in this
field or for those who want to start working there.
Within the spectrum of electromagnetic waves, the millimetre wave
range is located between the microwave range and the far-infrared
spectral region. The former may be characterized by the use of
technical components like solid state devices as sources, mixers or
detectors and by a circuit network (waveguides). For the far-infrared
region, on the other hand, it is typical to use optical components like
interferometers (Fabry-Perot or Michelson) and plane, spherical or
even aspherical mirrors. In the millimetre wave range, at the boundary
between these two, it is customary to employ a mixture of both
techniques. This is also demonstrated in this book with the description
of millimetre wave spectrometers and their components where the
authors prefer the language and terminology of microwave
techniques to that of optics. With respect to the physics at
millimetre wavelengths, one can observe magnetic excitations in
solids, e.g. antiferromagnetic resonance, and rotational transitions in
gases. The monograph discussed here is devoted to the latter
processes and to a very accurate measurement of the absorption lines
due to rotational transitions in order to determine the concentration of
the gas under investigation, i.e. to perform a quantitative analysis.
Consequently, it is helpful and convenient for the reader that
Chapter 1 of this monograph starts with a brief and concise
introduction to the theory of the interaction of millimetre wave
radiation with gases including the basic spectroscopic facts and
the various mechanisms of line broadening in gases. Finally, the
theoretical considerations lead to the different line profiles,
to the line intensity, i.e. the area under an absorption line,
and to the peak absorption coefficient αmax.
The absorption coefficient occurs rather frequently in the text
but the reader will be irritated by its notation changing
from the normal Greek letter α to γ on pages 2, 68 and
69 without any explanation. It is even more confusing that
γmax
appears in equation (4.8) with reference to equation (4.2) where the peak
absorption coefficient is written as αmax.
In Chapters 2, 3 and 5, an overview is presented of the components
for millimetre wave spectrometry, such as Fabry-Perot interferometers,
sources or detectors, and of commercially available spectrometers. A
more detailed discussion is provided of the millimetre
wave spectrometer designed and built by the authors and of its
components. The aim of this spectrometer is to
be compact, low-cost, automatic and robust. A confocal
Fabry-Perot interferometer (or cavity) is used as the sample cell in
order to provide a sufficient effective path length for sensitive
measurements on gases. The source is a frequency-stabilized Gunn
oscillator with a YIG oscillator as intermediate frequency source. The
source is frequency-modulated, and for phase-coherent detection of the
signal a He-cooled InSb bolometer or a Schottky diode mixer is used.
As far as the mechanical parts are concerned, i.e. the optical and technical
components, this spectrometer looks relatively simple. However, great
effort was required for the electronics and the control devices of this
instrument. The reader learns, for example, from the explanations in
Chapters 2 and 6 that it is necessary to drive one of the interferometer
mirrors synchronously to the frequency modulation of the source by
means of a piezoelectric actuator in order to keep the interferometer
always in resonance in the course of the frequency changes due to the
modulation of the source.
The performance of the authors' spectrometer and some of the results
obtained with it are summarized in Chapters 4 and 6. From the
discussion of the various mechanisms of line broadening and the
resulting absorption line profiles, e.g. Lorentzians, Gaussians or
combinations of both, it becomes obvious to the reader that the
dependence of the absorption line intensities on the concentration is
strictly linear while the corresponding data for the peak absorption
value exhibit a slight curvature. This is demonstrated in
figure 4.1 for
nitrous oxide (N2O) in air. Many other experimental data provide
convincing evidence of the capability of this millimetre wave
spectrometer for the quantitative analysis of gas mixtures. Moreover,
digital modulation techniques are also presented in Sections 4.1 and
4.2, replacing the sinusoidal frequency modulation, and these
allow simpler expressions to be obtained for the spectral signal.
In conclusion, this monograph is really an excellent up-to-date
introduction to the field of millimetre wave spectrometry and to
the quantitative analysis of gases by means of measurements in
this spectral range. Most details are based on the authors' own
experience with their home-made spectrometer, but other
approaches to the solution of the problems are also discussed.
Therefore, this monograph can be recommended for all scientists
interested in this field, working there or starting to work
there. That means not only chemists but also physicists and
scientists involved in environmental problems. Of course, this
compact monograph (118 pages) cannot deal with all technical
details, but the interested reader will most probably find an
answer to his questions in the references at the end of each
chapter.
Reinhart Geick