ABSTRACT
A new sample introduction system for the analysis of continuously flowing liquid streams by flame infrared-emission (FIRE) spectrometry has been developed. The system uses a specially designed purge cell to strip dissolved CO(2) from solution into a hydrogen gas stream that serves as the fuel for a hydrogen/air flame. Vibrationally excited CO(2) molecules present in the flame are monitored with a simple infrared filter (4.4 mum) photometer. The new system can be used to introduce analytes as a continuous liquid stream (process analysis mode) or on a discrete basis by sample injection (flow injection analysis mode). The key to the success of the method is the new purge-cell design. The small internal volume of the cell minimizes problems associated with purge-cell clean-out and produces sharp, reproducible signals. Spent analytical solution is continuously drained from the cell, making cell disconnection and cleaning between samples unnecessary. Under the conditions employed in this study, samples could be analyzed at a maximum rate of approximately 60/h. The new sample introduction system was successfully tested in both a process analysis- and a flow injection analysis mode for the determination of total inorganic carbon in Waco tap water. For the first time, flame infrared-emission spectrometry was successfully extended to non-volatile organic compounds by using chemical pretreatment with peroxydisulfate in the presence of silver ion to convert the analytes into dissolved carbon dioxide, prior to purging and detection by the FIRE radiometer. A test of the peroxydisulfate/Ag(+) reaction using six organic acids and five sugars indicated that all 11 compounds were oxidized to nearly the same extent. Finally, the new sample introduction system was used in conjunction with a simple filter FIRE radiometer as a detection system in ion-exchange high-performance liquid chromatography. Ion-exchange chromatograms are shown for two aqueous mixtures, one containing six organic acids and the second containing six mono-, di-, and trisaccharides.
ABSTRACT
A new type of wavelength dispersion system for use with a multichannel detector has been developed for simultaneous multielement analysis. The system employs a monochromator with fixed grating position, and incident angle varied by horizontal displacement of the entrance slits. The overlapping spectral windows which result can be arranged to produce a composite spectrum having minimal interference from emissions by other sample constituents. Entrance slits may also be displaced vertically to create a two-dimensional system in which spectra are stacked one above the other and scanned by use of a multi-raster scanning pattern. A number of optical and performance characteristics of the system are evaluated in both the one- and two-dimensional modes, and the system is applied to the determination of Ca, Na and K in blood serum and to the determination of the exchangeable cations Ca, Na, Li and K in clay. The advantages of this system for simultaneous multielement analysis are discussed.
ABSTRACT
A new type of programmed-scan monochromator that employs a multiple entrance-slit dispersion system with stationary dispersion optics has been assembled and tested. The instrument uses an optical multiplexer, connected to the multiple entrance-slit spectrometer (MESS) by means of fiber-optic light guides, to illuminate up to eight entrance slits sequentially. A single high-sensitivity relatively inexpensive photomultiplier tube is used as the detector. A microcomputer interfaced with the detector is used to acquire data at a rate of approximately 4 sec per element and to control the optical multiplexer. Detection limits obtained from atomic emission measurements with an acetylene/air flame excitation source are reported for lithium, sodium, calcium, barium and strontium. The influence of signal averaging and sampling rate on system performance has been studied, and it was found that the delay time had essentially no influence on the measured signal-to-noise ratio.
ABSTRACT
The reproducibility of a programmed-scan monochromator with stationary dispersion optics was evaluated by means of analysis of variance (ANOVA). The spectrometer used an optical multiplexer coupled with glass-fiber optic light-guides to a multiple entrance-slit spectrometer employing a photomultiplier as the detector. With this spectrometer, 15 emission intensity measurements at the lithium resonance line wavelength (670.7 nm) were collected for five rotations of the optiplexer mirror under four different emission situations: flame background emission at 670.7 nm, lithium emission from an acetylene-air flame in the absence of an ionization buffer, lithium emission from an acetylene-air flame in the presence of an ionization buffer, and tungsten lamp emission at 670.7 nm. For all four situations, the ANOVA results showed that instrumental changes which occurred during mirror rotation in the optiplexer were a significant source of signal variation compared with factors not associated with mirror rotation, i.e., photon shot noise, source fluctuation noise, and electronic drift. The actual magnitude of the signal variability introduced during mirror rotation, however, was found to be quite small, producing an average relative standard deviation of only 0.76% for the signal.
ABSTRACT
The feasibility of determining chlorinated, purgeable organic compounds (POCs) in aqueous samples by flame infrared-emission (FIRE) spectrometry was evaluated with a specially designed, multichannel, dispersive spectrometer having sufficient resolving power to prevent interference from large amounts of non-halogenated POCs that could also be present in the sample. The polychromator was based on a Czerny-Turner optical mounting with a 0.15-m focal length, a nominal focal ratio of f/3, and a reciprocal linear dispersion of 0.15 mum/mm in the first order. The HCl and CO(2) infrared emission bands (3.77 and 4.42 mum, respectively) were monitored in two analytical channels, while a third reference channel, used for background subtraction, monitored the H(2)O background emission at 2.8 mum. Instrumental performance was evaluated with dichloromethane, trichloromethane, trichloroethylene, 1,1,2,2-tetrachloroethane and monochlorobenzene as test compounds, and parameters such as the linear dynamic range, reproducibility, detection limit and signal-to-noise ratio, and extent of spectral crosstalk between channels were determined. The feasibility of performing a quantitative analysis of a two-component mixture of dichloromethane and trichloromethane at trace levels was demonstrated.
ABSTRACT
An isotope dilution method for the determination of chloride ion in aqueous samples is described. The method makes use of the isotopic shift in the rotational lines of the 1-0 band of HCl emitted in the near infrared region of the spectrum by vibrationally excited HCl molecules present in a hydrogen/entrained air flame. Chloride ion in the sample is converted to chlorine gas by electrolysis and swept into a hydrogen/entrained air flame where it is converted into HCl. Because isotope dilution is an absolute method of analysis, matrix effects are minimized, and the chlorine generation step need not be quantitative. With the system described in this paper, samples must contain at least 9 mg of chloride ion per ml, and a 2-ml sample is required. Over the range from 10 to 30 mg Cl(-) ml(-1), the average error was -0.96%, and the average relative standard deviation was 3.3% for seven samples using seven of the more intense lines in the P branch. Compared with standard silver nitrate titrations, the isotope dilution procedure was not affected by such common interferences as bromide ion and iodide ion. The technique was applied to several seawater samples from different regions.