Cells, sample

Connecting tube A Is made from 6mm OD pyrex and after exiting through the bath lid Is joined by means of a glass-metal seal. 

ACS Symposium Series American Chemical Society Washington, DC, 1975. 

In an experiment two of the sample vessels contain the two different Isotopic solutions. The pressure difference between them is monitored to approximately. 03% or 11).001 mm, whichever Is larger. The other two vessels contain a solution of the normal Isomer being compared against a standard solution, pure solvent, or vacuum. One run over the temperature range therefore furnishes us with a set of data on the total pressure and the Isotopic pressure ratio as a function of temperature. 

The calorimetric measurements were carried out either on an Isoperibol solution calorimeter built by us following conventional 

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A 5.00 X 10 M solution of an analyte is placed in a sample cell that has a pathlength of 1.00 cm. When measured at a wavelength of 490 nm, the absorbance of the solution is found to be 0.338. What is the analyte s molar absorptivity at this wavelength ... 

Infrared spectroscopy is routinely used for the analysis of samples in the gas, liquid, and solid states. Sample cells are made from materials, such as NaCl and KBr, that are transparent to infrared radiation. Gases are analyzed using a cell with a pathlength of approximately 10 cm. Longer pathlengths are obtained by using mirrors to pass the beam of radiation through the sample several times. 

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. 

Quantitative Analysis Using the Method of Standard Additions Because of the difficulty of maintaining a constant matrix for samples and standards, many quantitative potentiometric methods use the method of standard additions. A sample of volume, Vx) and analyte concentration, Cx, is transferred to a sample cell, and the potential, (ficell)x) measured. A standard addition is made by adding a small volume, Vs) of a standard containing a known concentration of analyte, Cs, to the sample, and the potential, (ficell)s) measured. Provided that Vs is significantly smaller than Vx, the change in sample matrix is ignored, and the analyte s activity coefficient remains constant. Example 11.7 shows how a one-point standard addition can be used to determine the concentration of an analyte. 

UV/Vis detectors are among the most popular. Because absorbance is directly proportional to path length, the capillary tubing s small diameter leads to signals that are smaller than those obtained in HPLC. Several approaches have been used to increase the path length, including a Z-shaped sample cell or multiple reflections (Figure 12.44). Detection limits are about 10 M. 

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... 

Photometric Moisture Analysis TTis analyzer reqiiires a light source, a filter wheel rotated by a synchronous motor, a sample cell, a detector to measure the light transmitted, and associated electronics. Water has two absorption bands in the near infrared region at 1400 and 1900 nm. This analyzer can measure moisture in liquid or gaseous samples at levels from 5 ppm up to 100 percent, depending on other chemical species in the sample. Response time is less than 1 s, and samples can be run up to 300°C and 400 psig. 

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. 

Figure 4.1-1 Liquid sample cells made from (a) TiZr alloy and (b) vanadium.

Sample cells include Lindemann/capillary tubes (normally < 1 mm in diameter) and aluminium holders. In the latter, thin aluminium windows sandwich the sample in a cylindrical aluminium sample holder. The diffraction from the aluminium is observed in this case, and may be used as a calibration standard. For low-temperature materials, the aluminium window can be replaced by the polymer Kapton. Beryllium may also be used [14]. Sample volumes of between 50 and 100 pL are typically required. 

The deflection refractometer (Fig. 8.4), which measures the deflection of a beam of monochromatic light by a double prism in which the reference and sample cells are separated by a diagonal glass divide. When both cells contain solvent of the same composition, no deflection of the light beam occurs if, however, the composition of the column mobile phase is changed because of the presence of a solute, then the altered refractive index causes the beam to be deflected. The magnitude of this deflection is dependent on the concentration of the solute in the mobile phase. 

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. 

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