The development of ionic methods for the determination of corrosion products in the highly radioactive Homogeneous Reactor (HR) fuels has been of major interest in the work of the Ionic Analyses Laboratory. Methods for the spectrophotometric determination of aluminum and for the polarographic determination of iron in HR fuels have been developed. The polarographic determination of molybdenum in uranyl sulfate solutions was studied. A polarographic method for the determination of zinc was developed. A fluorometric method for the determination of microgram amounts of fluoride was studied. Three organic reagents were investigated as precipitants for microgram quantities of zirconium in HR fuel. The automatic photometric titration technique was applied to the determination of thorium and of sulfate. A method was developed for the ionexchange separation and potentiometric titration of cobalt. The ultraviolet absorption spectra of technetium and rhenium were studied.

Bench scale studies have been made of the recovery of uranium from acid leach liquors (and slurries) by solvent extracting with di (2-ethylhexyl) phosphoric acid in an organic diluent. Uranium may be stripped from the organic solvent by either alkaline or acidic reagents, the former having been studied in greater detail. On the basis of these tests, a recovery process may be considered which shows promise both from the standpoint of operation and chemical costs. Under proper conditions, vanadium can also be extracted by the di (2-ethylhexyl) phosphoric acid and stripping again may be accomplished with either acidic or alkaline reagents. Preliminary studies have been made of these possibilities. In addition to di (2-ethylhexyl) phosphoric acid, some other organophosphorus acids, have been cursorily examined in respect to their extraction and/or stripping performance.

New systems involving the exchange of boron between boron trifluoride and boron trifluoride addition compounds have been explored. These systems have large separation factors and potentially simple reflux mechanisms. A precise determination of this separation factor for the anisole-boron trifluoride system gave the value (see report). Boron exchange was found to occur between BF and BCl3. Several homogenous catalysts have been found which activate the hydrogen-water exchange, but none are adoptable to the production of deuterium because of the slow exchange rate. Platinum or platinum oxide may be usable as a heterogeneous catalyst with proper support or dispersion techniques. The high-pressure solubility of hydrogen in several amalgams was investigated in connection with a unique countercurrent exchange system. A proposed system involving isotopic exchange between lithium dipivaloylmethane in diethyl ether and lithium hydroxide in aqueous solution was shown to give little or no isotopic separation. Column studies of the carbonate system exchange reaction were concluded with a 40°C run. Slightly higher enrichment of N15 was obtained than at 30°C . The temperature dependence of all in this system was measured between 15 and 45°C. The factor increases with temperature, showing a tendency toward a maximum near 45°C. Isotopic exchange appears to …

The conversion of UNH to UF4 and UF6, utilizing moving-bed techniques, is being studied; sufficient progress has been made that an evaluation of the process is warranted. The procedures under study, the Fluorox Process, have three major advantages: (1) substitution of HF for high-cost fluorine, (2) considerable reduction in HF requirements, and (3) marked reduction in plant-size and mechanical complexity.

A new gas-liquid countercurrent system (the ANCO system from Anisole-Complex) for the enrichment of boron isotopes has been developed. It is believed that use of this systems will result in a considerably lower unit cost for enriched boron-10 than was previously possible. The system utilizes the exchange reaction between BF3 (gas) and BF3·anisole (liquid) to concentrate boron-10 in the liquid phase. The single stage isotopic separation factor for this system has been found to vary from 1.039 at 0°C to 1.029 at 30°C. The isotopic exchange reaction has been shown to be rapid. Vapor pressures of the complex as a function of temperature have been measured and the heat of formation of the complex determined. Laboratory experiments show that quantitative removal of the BF3 from the complex can be accomplished by heating. A complete miniature ANCO plant was constructed and operated in the laboratory to test the feasibility of the system. The system was found to operate efficiently with a minimum of attention, and to enrich the isotopes of boron as expected. Based upon the experience obtained with the laboratory ANCO unit, a pilot plant large enough to utilize a 6-inch diameter exchange column was designed. The design calculations of …

Thorium, a fertile material, is of interest to the Reactor Program in the production of U233. Thorium can be extracted and processed to a very pure bulk metal for fabrication into solid fertile elements. There are advantages, technical and economic, for using fabricated bulk thorium dioxide rather than the metal in some applications. It is the purpose of this paper to point out these advantages and to present briefly the technology related to fabrication, radiation damage and chemical processing of ThO2.

Activity and ionic impurity specifications are presented for Thorex thorium nitrate products. Two sets of specifications are given, one set for direct handling during refabrication of production reactor thorium metal slugs and the second for refabrication of future power reactor thorium metal elements by semi-remote technics. Consideration was given to the health hazard problems associated with each process step between the Thorex process and final refabricated source material in order to arrive at these specifications.

Electrodialysis in an ion-exchange membrane cell was shown to be technically feasible for the concentration of an azeotropic mixture of HF and water. A flowsheet is presented for recovery of anhydrous HF by distillation and electrodialysis of the azeotropic residue. In the electrodialysis step, 2.6 kwhr of energy per pound of anhydrous product was consumed, with electricity at 1¢ per kilowatt-hour, the total operating cost of the electrodialysis equipment alone, including amortization, would be 6¢ per pound of HF.

This technical report described the formulation of a set of two-group neutron diffusion equations and the solution for the critical fuel cross section in a one-dimensional, multi-region spherical reactor. A subsequent report will describe the ORACLE code developed for survey calculations using this method.

Preliminary results of tests wit the Westinghouse 100A pump indicate that Al2)3 and tungsten carbide coated bearing-journal assemblies prepared by the Linde process are not promising as substitutes for the graphitar-stellite combination. The front Al2O3 assembly failed at start-up with water and both front and rear tungsten carbide assemblies failed after 121 hours with water at 245 C.

General considerations involving the transportation of irradiated fuel and radioactive wastes are reviewed. It is assumed that many reactors will supply feed to a few large multipurpose chemical plants which ultimately send radioactive waste to a few disposal sites. General economic considerations of irradiated fuel reprocessing, economic aspects of the nuclear economy complex, growth predictions of the nuclear power economy in the U.S., general requirements for the shipment of fuel and waste, regulations applicable to fuel shipment, and permissible radiation levels are discussed.

Stress corrosion was found in 8 components of the HRT mockup; only of four of these actually shut down the loop. All of the failures have occurred in the high-pressure system of the loop.

During the development of in-reactor corrosion experiments three types of bomb designs have been developed for following quantitatively the consumption of oxygen in a bomb which is fabricated from the particular metal under test. The bombs are designed so as to be rocked continuously during their in-reactor exposure, consequently agitating the uranium salt solution contained in the bomb and permitting gentle movement of the solution past metal specimens and other corroding surfaces. The oxygen pressure is produced within the bomb at the beginning of the run either by the withdrawal of gas from an oxygen tank or by the decomposition of hydrogen peroxide added just prior to closure. Temperature measurements are obtained by mans of thermocouples placed in a well within the bomb body or, in the latest design, there will also be thermocouples staked at several points on the outer wall of the bomb. The assembly is inserted in an experimental access hole in the reactor, brought up to a predetermined operating temperature by means of an electric furnace in close contact with the bomb, and allowed to remain for the desired amount of exposure to reactor radiation. Periodic measurements of temperature and pressure are made and the bomb …

The operation of the HRT mockup was on 0.042m UO2SO4, 0.024m H2SO4, and 0.005m CuSO4 at 280 C and 1400 psi pressure. with the O2 content at near 500 ppm. The pump showed bearing wear and high corrosion. The letdown heat exchanger was removed from the mockup and sectioned. The metallographic examination revealed corrosion. Results of corrosion runs on Ti, zircaloy-2, and stainless steel are given.

Results of previous toroid tests with 28 micro 1600 fired ThO2 spheres are analyzed. Four possible explanations for the essentially zero attack rates are offered and discussed: peculiar motion of toroids or some unknown wall effect; rotational hydrodynamic forces cushioning the particle impact; the bed was not in suspension and not sliding over the walls of the toroid; round particles are not as erosive to oxide film surface as sharp pointed particles.

The leak detector system consists of one gas pressurized reservoir containing heavy water, a tubing manifold connecting the pressurizer to six separate lines each connected to one of the flanges, tubing lines leading from the second hole on each of three flange pairs (dome and heat exchanger flanges) back into the instrument room, plus required valves and fittings. A schematic diagram of the system in included.

Calculations indicate that it is impossible, even at high oxygen injection rates, to insure an excess of oxygen in the HRT fuel solution if the bubble letdown rate is more than 1 or 2 liters per minute. If, on the other hand, no bubbles are allowed to form, a reasonable excess oxygen concentration can be maintained with an oxygen injection rate which would not tax the capacity of the off-gas system. The xenon poison will be reduced to less than 2% by liquid letdown alone, and if an iodine absorption bed is installed below the catalytic recombiner, the xenon poison should be less than 1% without any bubble letdown. Therefore, it is recommended that sufficient copper be added to prevent the formation of gas bubbles and that the oxygen injection rate be limited to a value which would permit adequate holdup times in the present charcoal adsorption beds, assuming this quantity is sufficient to meet corrosion requirements.

To better understand the solvent extraction process much effort has been and is being expended at ORNL and elsewhere to measure reaction kinetics of the extraction reactions. To date these efforts have been largely unsuccessful, due to the attempt to apply homogeneous reaction kinetics to two-phase systems. An optical method has been devised for analyzing the concentration profile in the vicinity of a quiescent interface during steady-state diffusion at rather large molecular fluxes. The system under study is the extraction of uranyl ion from water by a TBP solution. Considerable effort has been directed to eliminating leaks in the diffusion cell and testing the optical system/

In order to make rational predictions of the operating characteristics of uranium anion exchange contactors, an understanding of the mechanism and kinetics of the exchange is necessary. Toward this objective an effort is being made to determine the equilibrium sorption isotherms and rates of sorption of uranium on the anion exchange resin Dovex 21K.

In order to make rational predictions of the operating characteristics of uranium anion exchange contactors, an understanding of the mechanism and kinetics of the exchange is necessary. Toward this objective an effort is being made to determine the equilibrium sorption isotherms and rates of sorption of uranium on the anion exchange resin Dovex 21K.

A study of the thermodynamic properties of dilute aqueous hydrochloric acid solutions at elevated temperatures by an electromotive force method was undertaken for several reasons. First, a great need for fundamental information at elevated temperatures was evident from the growing number of industries making use of aqueous solutions at elevated temperatures. Second, the use of the hydrogen electrode against the silver-silver chloride electrode in dilute hydrochloric acid solutions promised to give fundamental thermodynamic information on an important electrode system as well as on hydrochloric acid over a wide temperature range.

Considerable delay has occurred in getting ratification of the Eurochemic charter by 80% of the participating nations. The French, who were not expected to ratify the charter until an elected government was again established , actually ratified under de Gaulle late in 1958.

A study was made of a method for the flame photometric determination of iron. In Part I of this report, the flame emission spectrum of iron, measured by means of a Beckman Model DU spectrophotometer with a flame attachment, is compated to that measured with an ORNL high-sensitivity, recording, single-beam instrument, in order to determine which instrument is best suited for this application. Although it was found that the Beckman product has the higher resolving power over the wavelength region of 360 to 400mu, it does no posses the sensitivity or ease of operation of the ORNL instrument. On this basis, the ORNL flame spectrophotometer is used in subsequent tests. After selecting the best-suited instrument for the flame photometric determination of iron, it was necessary to establish the optimum operating conditions for this particular method. These conditions are described in Part II.

The technique of high-frequency titrimetry has been applied to the determination of thorium, uranium, sulfate, and free acid. In Part I of this report, the reproducibility of the method for the titration of standard solutions which contained 50mg of thorium in the absence of interferences is established. The coefficient of variation of the method, under these conditions, was found to be less than one per cent. In Part II, the effect of uranium on the high-frequency titration of thorium, as well as the application of the method to actual samples, is discussed. Uranium in a ratio of 5 to 1 to thorium can be tolerated. When the method is applied to the analysis of representative samples, the coefficient of variation is one per cent.