Chemical measurements with optical fibers for process control.

Several aspects of remote in situ spectrophotometric measurement by means of optical fibers are considered in the context of chemical process control. The technique makes it possible to measure a species in a particular oxidation state, such as plutonium(VI), sequentially, under the stringent conditions of automated analysis. For the control of several species in solution, measurements at discrete wavelengths on the sides of the absorption peaks serve to increase the dynamic range. Examples are given concerning the isotopic separation of uranium in the Chemex process. The chemical control of complex solutions containing numerous mutually interfering species requires a more elaborate spectral scan and real-time processing to determine the chemical kinetics. Photodiode array spectrophotometers are therefore ideal for analysing the uranium and plutonium solutions of the Purex process. Remote on-line control by ultraviolet monitoring exhibits limitations chiefly due to Rayleigh scattering in the optical fibers. The measurement of pH in acidic (0.8-3.2) and basic media (10-13) has also been attempted. Prior calibration, signal processing and optical spectra modeling are also discussed.