Double-beam

A comparison between the beam intensity before and after the flame provides a measurement of the quantity of photons absorbed and therefore the concentration of the atom being analyzed. The comparison can be made directly by a double beam analyzer. See Figure 2.7 in which the beam is divided into 2 branches one of which traverses the flame, the other serving as... 

Block diagram for a double-beam in-time scanning spectrophotometer with photo of a typical instrument. 

Infrared instruments using a monochromator for wavelength selection are constructed using double-beam optics similar to that shown in Figure 10.26. Doublebeam optics are preferred over single-beam optics because the sources and detectors for infrared radiation are less stable than that for UV/Vis radiation. In addition, it is easier to correct for the absorption of infrared radiation by atmospheric CO2 and 1420 vapor when using double-beam optics. Resolutions of 1-3 cm are typical for most instruments. 

Atomic absorption spectrophotometers (Figure 10.37) are designed using either the single-beam or double-beam optics described earlier for molecular absorption spectrophotometers (see Figures 10.25 and 10.26). There are, however, several important differences that are considered in this section. 

Figure 3.23 A typical double-beam recording mid-infrared and near-infrared spectrophotometer...

Fig. 25-2. Double-beam, double-pass transmissometer for measuring smoke density in stacks. A[, chopper wheel A, beam gating wheel A3, aperture D, detector Fj, spectral filter F2, solenoid-activated neutral density filter L, lamp M, half-mirror/beam splitter Rj, solenoid-activated zero calibration reflector R2, retroreflector (alignment bullseye not shown). Design patented. Source Drawing courtesy of Lear Siegler, Inc.

Double-beam spectrophotometers. Most modern general-purpose ultraviolet/ visible spectrophotometers are double-beam instruments which cover the range between about 200 and 800 nm by a continuous automatic scanning process producing the spectrum as a pen trace on calibrated chart paper. 

The absorbance and the percentage transmission of an approximately 0.1M potassium nitrate solution is measured over the wavelength range 240-360 nm at 5 nm intervals and at smaller intervals in the vicinity of the maxima or minima. Manual spectrophotometers are calibrated to read both absorbance and percentage transmission on the dial settings, whilst the automatic recording double beam spectrophotometers usually use chart paper printed with both scales. The linear conversion chart, Fig. 17.18, is useful for visualising the relationship between these two quantities. 

Procedure. The study can be carried out using either a manually operated single-beam spectrophotometer, or an automatic recording double-beam spectrophotometer. In both cases the wavelengths at which HMR and MR-exhibit absorption maxima are readily obtained from the spectra. 

The deuterium arc continuum travels the same double-beam path as does the light from the resonance source (see Fig. 21.9). The background absorption affects both the sample and reference beams and so when the ratio of the intensities of the two beams is taken, the background effects are eliminated. 

A large number of commercial instruments are now available and are based either on a single- or double-beam design. Important instrumental features of a modem atomic absorption instrument include the following facilities. 

Double-beam AA spectrophotometers are still marketed by instrument manufacturers. A double-beam system compensates for changes in lamp intensity and may require less frequent re-zeroing than a single-beam instrument. These considerations had more merit some years ago when hollow cathode lamps suffered from some instability. It should be noted, however, that the optical... 

A double-beam atomic absorption spectrophotometer should be used. Set up a vanadium hollow cathode lamp selecting the resonance line of wavelength 318.5 nm, and adjust the gas controls to give a fuel-rich acetylene-nitrous oxide flame in accordance with the instruction manual. Aspirate successively into the flame the solvent blank, the standard solutions, and finally the test solution, in each case recording the absorbance reading. Plot the calibration curve and ascertain the vanadium content of the oil. 

Spectrographically standardised substances 830 Spectrophotometer cells for, 664 data presentation, 665 double-beam, 667 layout of instruments, 666, 667 operation of, 672 radiation sources for, 664 single-beam, 666... 

Two identical reaction solutions were prepared, one at T,(= 25.000 °C) in the sample compartment of a double-beam spectrophotometer, the other at T2( = 27.170 °C) in the reference beam. A direct recording of AAbs = Absi - Abs2 was made as a function of time while the difference in reaction temperature was maintained to 0.0001 °C. Evaluate kffk and AW1 for the run shown note this calculation is possible with an arbitrary time axis. 

Recent work in our laboratory has shown that Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) can be used routinely to measure vibrational spectra of a monolayer on a low area metal surface. To achieve sensitivity and resolution, a pseudo-double beam, polarization modulation technique was integrated into the FT-IR experiment. We have shown applicability of FT-IRRAS to spectral measurements of surface adsorbates in the presence of a surrounding infrared absorbing gas or liquid as well as measurements in the UHV. We now show progress toward situ measurement of thermal and hydration induced conformational changes of adsorbate structure. The design of the cell and some preliminary measurements will be discussed. 

Because process mixtures are complex, specialized detectors may substitute for separation efficiency. One specialized detector is the array amperometric detector, which allows selective detection of electrochemically active compounds.23 Electrochemical array detectors are discussed in greater detail in Chapter 5. Many pharmaceutical compounds are chiral, so a detector capable of determining optical purity would be extremely useful in monitoring synthetic reactions. A double-beam circular dichroism detector using a laser as the source was used for the selective detection of chiral cobalt compounds.24 The double-beam, single-source construction reduces the limitations of flicker noise. Chemiluminescence of an ozonized mixture was used as the principle for a sulfur-selective detector used to analyze pesticides, proteins, and blood thiols from rat plasma.25 Chemiluminescence using bis (2,4, 6-trichlorophenyl) oxalate was used for the selective detection of catalytically reduced nitrated polycyclic aromatic hydrocarbons from diesel exhaust.26... 

Rosenzweig, Z. and Yeung, E. S., Laser-based double-beam circular dichroism detector for liquid chromatography, Appl. Spectr., 47, 207, 1993. 

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