The Sample Cell

Since o-phenanthroline is present in large excess (2000 xg of o-phenanthroline for 100 xg of Fe +), it is not likely that the interference is due to an insufficient amount of o-phenanthroline being available to react with the Fe +. The presence of a precipitate in the sample cell results in the scattering of radiation and an apparent increase in absorbance. Since the measured absorbance is too high, the reported concentration also is too high. 

Finally, values of sx are directly proportional to transmittance for indeterminate errors due to fluctuations in source intensity and for uncertainty in positioning the sample cell within the spectrometer. The latter is of particular importance since the optical properties of any sample cell are not uniform. As a result, repositioning the sample cell may lead to a change in the intensity of transmitted radiation. As shown by curve C in Figure 10.35, the effect of this source of indeterminate error is only important at low absorbances. This source of indeterminate errors is usually the limiting factor for high-quality UV/Vis spectrophotometers when the absorbance is relatively small. 

Sensitivity The sensitivity of a molecular absorption analysis is equivalent to the slope of a Beer s-law calibration curve and is determined by the product of the analyte s absorptivity and the pathlength of the sample cell. Sensitivity is improved by selecting a wavelength when absorbance is at a maximum or by increasing the pathlength. 

The sample cells for molecular fluorescence are similar to those for optical molecular absorption. Remote sensing with fiber-optic probes (see Figure 10.30) also can be adapted for use with either a fluorometer or spectrofluorometer. An analyte that is fluorescent can be monitored directly. For analytes that are not fluorescent, a suitable fluorescent probe molecule can be incorporated into the tip of the fiber-optic probe. The analyte s reaction with the probe molecule leads to an increase or decrease in fluorescence. 

In FT-Raman spectroscopy the radiation emerging from the sample contains not only the Raman scattering but also the extremely intense laser radiation used to produce it. If this were allowed to contribute to the interferogram, before Fourier transformation, the corresponding cosine wave would overwhelm those due to the Raman scattering. To avoid this, a sharp cut-off (interference) filter is inserted after the sample cell to remove 1064 nm (and lower wavelength) radiation. 

Figure 9.22 illustrates how a CARS experiment might be carried out. In order to vary (vj — V2) in Equation (9.18) one laser wavenumber, Vj, is fixed and V2 is varied. Here, Vj is frequency-doubled Nd YAG laser radiation at 532 nm, and the V2 radiation is that of a dye laser which is pumped by the same Nd YAG laser. The two laser beams are focused with a lens L into the sample cell C making a small angle 2a with each other. The collimated CARS radiation emerges at an angle 3 a to the optic axis, is spatially filtered from Vj and V2... 

The primary reference method used for measuring carbon monoxide in the United States is based on nondispersive infrared (NDIR) photometry (1, 2). The principle involved is the preferential absorption of infrared radiation by carbon monoxide. Figure 14-1 is a schematic representation of an NDIR analyzer. The analyzer has a hot filament source of infrared radiation, a chopper, a sample cell, reference cell, and a detector. The reference cell is filled with a non-infrared-absorbing gas, and the sample cell is continuously flushed with ambient air containing an unknown amount of CO. The detector cell is divided into two compartments by a flexible membrane, with each compartment filled with CO. Movement of the membrane causes a change in electrical capacitance in a control circuit whose signal is processed and fed to a recorder. 

In Table 4.3, the Cetac product LSX-200 is the specialized system for coupling with the ICP customer s system. It includes the laser, optical viewing system for exact positioning of the laser focus on a sample surface, and the sample cell mounted on the computer controlled XYZ translation stage. The system is also provided with the appropriate gas tuhing for transport of the ablated material into an ICP-OES/MS. 

In many industrial gas measurements, water vapor is present in high concentrations. The sample cell of the measurement instrument and sample line can be heated up to 200 °C to remove water vapor. Sometimes, the sample gas is dried by condensation or by using Peltier gas dryers. 

In these instruments the monochromated beam of radiation, from tungsten and deuterium lamp sources, is divided into two identical beams, one of which passes through the reference cell and the other through the sample cell. The signal for the absorption of the contents of the reference cell is automatically subtracted from that from the sample cell giving a net signal corresponding to the absorption for the components in the sample solution. 

A Q-switched Nd YAG laser (7 ns pulse duration, Quanta-Ray DRC-1A) operated at 10 Hz was used as a light source. The 1064 nm fundamental was frequency doubled to 532 nm for some experiments. In all experiments reported here a geometry was used which focused the laser beam in front of the entrance window of the sample cell such that the laser beam was diverging as it passed through the sample cell. In this geometry the laser beam was about 3 mm in diameter at the region viewed by the light detection system. 

Photodecomposition. A greyish-white film of solid material slowly formed along the bottom of the sample cell in PuF6 cells irradiated at 1064 nm. A similar film formed considerably faster in sample cells irradiated at 532 nm with the film forming on the entrance face of the cells as well as along the walls of the cell. Film formation was evident after less than a minute of irradiation at a laser fluence of 5 J/cm2 at 532 nm. The exact chemical composition of the film has not yet been determined. It is known that it contains plutonium and... 

The output of a differential scanning calorimeter is a measure of the power (the rate of energy supply) supplied to the sample cell. The thermogram in the third illustration shows a peak that signals a phase change. The thermogram does not look much like a heating curve, but it contains all the necessary information and is easily transformed into the familiar shape. 

The differential refractometer monitors the deflection of a light beam caused by the difference in refractive index between the contents of the sample cell and those of the reference cell. A beam of light from an... 

Deviation refractometers are the most commonly used. This version of the DRI measures the deflection in the location of a light beam on the surface of a photodiode by the difference in refractive index between the polymer solution and pure solvent. The Fresnel-type refractometers operate on the principle that the intensity of light reflected from a glass-liquid interface is dependent on the incident angle and the RI difference between the two phases. The deviation and Fresnel detectors typically have cell volumes of 5 to 10 pi, detection limits of about 5 x 10-6 refractive index units (RIU), and a range of 10 7 to 10 3 RIU.156 The deflection-type DRI is relatively insensitive to the buildup of contaminants on the sample cell and is therefore of special utility in laboratories that process large numbers of samples, such as industrial laboratories. 

In the latter procedure, which is often called oscillometry6, one observes the frequency at which resonance occurs or one retunes the oscillator to the original frequency, e.g., with the aid of a calibrated capacitor parallel to the sample cell. Further, in oscillometry it is useful to compare in parallel with a reference frequency unit. 

The fluid from the tube or the core leaves the valve through port 5 and enters the inlet of the sample cell of the differential refractometer (made by Knauer of West Germany). The residue flows out of the sample cell to the waste. The reference cell contains... 

In order to study dynamic aspects of biomolecular structure, it is necessary to perform measurements over an appropriate temperature range. This is accomplished by directing dry air downward over the sample cell from the nozzle of a device used to cool protein crystals in X-ray... 

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