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Gilbraith, William E.

Publications and source records attributed to Gilbraith, William E..

Continued Evaluation of the Use of a Raman Spectrometer for H-Canyon Dissolver Monitoring

Remote monitoring of dissolver activities in H-Canyon can help operators avoid delays associated with excessive levels of fuel fragments remaining after a run. SRNL has proposed that effective monitoring can be achieved by using a Raman spectrometer to measure NO 2 concentrations in the offgas stream sampled from the facility stack. Prior work (SRNL-STI-2021-00451) measuring the offgas from one dissolution batch of High Flux Isotope Reactor (HFIR) fuel suggested a relationship between %NO 2 levels and fragment height. Herein, we report the results of monitoring and analysis of the dissolution of four batches of Material Test Reactor (MTR) fuel. A rigorous quantitative relationship between %NO 2 measurements and fragment heights could not be established, due to high uncertainties associated with both measurements. Uncertainties with gas measurements are associated with the %NO 2 levels in the offgas being close to the detection limit for the analyzer. Alternative gas measurement strategies are discussed which could improve sensitivity and reduce uncertainty. Limitations to the precision of the probe measurements are also discussed. It is also noted that the offgas is an average of the products from simultaneous dissolution of elements in multiple wells. Detection of a high fragment height level in an individual well may be hindered by low levels in other wells.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Disentangling Acid‐Base Chemistry through Blue Shifting Hydrogen Bond Contributions

The blue shifting of vibrational frequencies in hydrogen bonded molecules, as observed in aqueous environments, has been attributed to local partial charge transfer from solvation. Here, in this study, we extrapolate the blue shift model to the stronger ionic interactions between hydrogen bond acceptors associated with protonation through augmented pH levels and competitive interactions with counter ion pairing. The chemical model we utilize in this work is the aqueous pyridine‐pyridinium equilibrium to characterize the blue shifts observed in the pyridinium chloride ionic system. The observed agreement between observed experimental and calculated spectral shifts shows that the blue shifting model can be extrapolated to stronger interactions and accurately describe the nature of the hydrogen bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Instrument Control Software for Spectrophotometers

SRNL has developed instrument control software for diode array spectrophotometers that can be used for real time monitoring of dynamic systems. This software has evolved through several iterations as instruments have been developed for use in processing facilities at Savannah River Site. There are several noteworthy features of the software. The wavelength calibration is checked and updated in real time against reference emission lines that are designed into the instrument light source. Nonlinearities and offsets associated with the intensity response of the instruments are characterized, and absorbance spectra are appropriately corrected. These actions are necessary for accurate calculation of an absorbance spectrum from the intensity responses of two individual diode array detectors. The corrections also result in the spectra obtained for a particular sample by two (or more) different diode array detector pairs being nearly identical. This property assures consistent measurements at multiple locations with different instruments. It also permits the use of a single analyte calibration across many instruments without modification and without loss of accuracy

47 OTHER INSTRUMENTATION↗