Technical report covering (1) analysis of uranium bromide and chloride samples, (2) the ferric-nitrate method of analyzing uranium fluorides for fluorine, (3) spectrographic determination of boron, cadmium and manganese in magnesium metal, (4) service analyses. contributions to other problems, (5) attempted preparation of uranous oxyfluoride, and (6) corrections in previous reports.

Technical report. Areas covered are properties of uranium halides, properties of uranium nitrides, and hydride formation at high pressure.

Technical report with short articles on (1) Uranium-oxygen system compositions UO2 to U3O3; (2) Thorium hydride; (3) Production of cerium; and (4) Production of thorium.

Abstract. to estimate the oxygen picked up by thorium in casting a rapid method of running the acid insoluble content was developed. the quickest procedure consists of reacting with mixed acids, fuming with perchloric and filtration to separate the "free" thorium from the "combined". The precipitate is ignited and weighed as thorium dioxide.

Technical report discussing that the deuterium concentration of heavy water can be determined by equilibrating the water with deuterium gas in the presence of a catalyst with subsequent analysis of the equilibrated gas on the mas spectrometer. The apparatus for equilibration analyses maybe be considered in three parts: 1) apparatus for introducing the ingredients into the reaction chambers; 2) the reaction chambers; 3) the mass spectrometer for analysis of the equilibrated gas. The isotopic composition of the deuterium gas to be used as the starting material is primarily governed by what gases are available. In general it is best to use gas within about one percent on either side of the final equilibrium composition. No reaction takes place between deuterium gas and water molecules in the absence of a catalyst. Platinum oxide is used as the catalyst.

Introduction. the colorimetric determination of iron based on the formation of the colored ferrous-1,10-phenanthroline complex has been used successfully by a number of investigators. In this technical report, its adaptation to the routine determination of iron in cerium, thorium, and beryllium metals and their compounds is described.

Abstract. Methods of analysis for thorium, calcium, and nitric acid in solutions from thorium extraction purification columns are described and the results and errors are outlined. A brief description of methods of analysis that were not successful is included.

Introduction. the conventional procedures of analysis for uranium and manganese can be employed in the analysis of alloys of these metals. The alloys are reacted with perchloric acid and hydrogen peroxide, fumed to remove any chloride ions, diluted to volume and aliquots analyzed by redoximetry.

Abstract. Methods for determination of both uranium and nickel in solutions of these metals are described. Alloys can be dissolved in nitric acid treated with citric acid to complex the uranium, and the nickel precipitated as nicked dimethylglyoxime. The uranium is reduced and titrated with standard ceric sulfate. These methods are for the determination of macro amounts of uranium and nickel with errors on the order of 0.1%.

Technical report describing a gasometrical method for the determination of H2 in extruded U rods.

Technical report abstract. The present state of knowledge concerning the effect of pile radiation on a variety of solid materials is reviewed. Radiation corrosion will not be a serious hazard for aluminum or stainless steel but it can be for iron or lead if either are exposed to water. Apart from corrosion the principal uncertainty is in regard to the Wigner effect on the behavior of metals. There is at present no ground for optimism regarding the behavior of tuballoy. The effect on aluminum or a bonding material while less severe must also be considered serious. The expectation in regard to graphite is that its behavior will not cause trouble during the first 100 days of operation although serious troubles will probably arise within two years of operation. Organic materials can be used safely only in regions of limited exposure.

Abstract. The distribution coefficient of U(VI) between perchloric acid solutions and benzene solutions of TTA has been measured as a function of the acidity. It was possible to interpret the data in terms of the charge on the U(VI) species present in the aqueous phase. The experiments indicate that U(VI) exists as an ion charge +2 at acidities from 0.1M to 2.5M. In the interpretations of the distribution data, it was necessary to know the acidity coefficient of the uranyl chelate in the benzene solution. This was determined by measurement of the solubility of the compound UO2K2 - xH2). The activity coefficient of UO2K2 was found to decrease rapidly as the concentration of TTA in the benzene phase increased above 0.1M. This is probably due to the formation of a species involving more than two TTA molecules per U(VI)

Technical report containing short articles on (1) Determination of physical constants for U233; (2) Determination of decay chain of U233; (3) Extraction of U233; (4) Extracting solvents for uranium; (5) Factors affecting the extraction uranium and thorium by organic solvents, especially ether; and (6) Analysis of ore samples for protoactinium.

Abstract. The precipitation of Pa233 with MnO2 from a solution of thorium nitrate has been studied in some detail and seems quite satisfactory up to 36 gm Th(HO3)4 4H2O per 100 cc solution. The concentration of Pa233 with respect to the manganese dioxide carrier and the thorium precipitated with the carrier appears to be accomplished quite well by either a series of MnO2 cycles or thorium iodate cycles. Volatility methods for both the separation of Pa233 from the original thorium and for its separation from MnO2 are now under investigation. It has been decided that thorium carbonate will the the thorium compound used in the pile at Site X.

Technical report. Numerous application of various column adsorption techniques to inorganic analytical chemistry have appear in the literature. The comparatively recent introduction of ion exchange resins has resulted in the development of efficient, simple, and rapid column adsorption methods. the principal service of column adsorption methods to analytical chemistry is that of providing a relatively simple means of separating an element in a sufficiently pure state so that a direct precipitation, ignition, and weighting, for example, will suffice to complete the quantitative analysis. Systems involving uranyl nitrate will naturally be emphasized in this report but information will be included concerning the separation of the individual members of a series from one another, such as in the alkaline earths and the rare earths.

Abstract. In the first section of this technical report a new method of extracting uranium from thorium nitrate solution is discussed. This method consists of extracting an aqueous solution of thorium nitrate, nitric acid, sodium sulphate, and potassium thiocyanate with hexone. By this procedure, using an equal volume of hexone it is possible to extract 83 percent of the uranium while only 0.3 percent of the thorium is extracted. other experiments show that even greater separations are possible. In the second section of this report the use of antipyrine in solvent extraction procedures is discussed. Experiments are described in which 90 percent of the uranium is extracted while the thorium is extracted to the order of 3 to 5 percent.

Technical report on the studies that have been made on the composition and thermal decomposition of uranyl peroxide. The conditions of precipitation and drying have been found to have no appreciable effect on the composition of the compound, but do affect the physical appearance of the precipitate and the rate of thermal decomposition. The UO4 + 2H2O appears to be thermodynamically unstable with respect to UO3 at 25 degrees C and atmospheric pressure, although the rate of conversion is extremely slow. The UO4 + 2H2O is completely converted to UO3 on standing at 150 degrees C and atmospheric pressure for two weeks. Partially decomposed uranyl peroxide samples contain extra oxygen which is released on immersing the sample in water.

Technical report describing the investigation of the short-lived activities produced in oxygen compounds by irradiation with pile neutrons. The most prominent of these activities in cooling water is a beta and gamma emitting activity of about 8 second half-life. Because of its production by epicadmium neutrons it was believed to be the 8 second N16 produced in the pile by n,p on O16. The identification has been accomplished and it is established that the 8 second activity is N16. Part 2 of the report deals with the determination of the recoil range of the Al28 atoms formed by pile n,p reaction on Al27.

Introduction. Some forty different uranium compounds have now been given diffraction study at Ames. Reports of these investigations are scattered in the Project literature; many have been reported in a sentence or two as a note along with chemical or metallographic reports. To make the results of this crystal structure work more available this summary of the Ames work has been compiled. (A similar summary has already been published from the Chicago laboratory.)

Technical report abstract: Since UNH is a highly dissociated compound which ionizes to NO3 and (UO2), the latter ion being very weakly basic, a solution of pure UNH is quite acid (pH about 3). It is possible to titrate to a phenolphthalein and point with standard caustic solution and obtain a figure which represents the free acid plus the NO3 from the the UNH. However, titration of the free nitric acid alone in such a solution presents quite a problem. By precipitating and removing uranium from solution by means of potassium ferrocyanide, the residual free acid may be titrated directly by means of standard caustic using either methyl red or phenolphthalein indicators, with an error of less than 4%. A method is given to determine formic acid, should that acid be present in the mixture.

Technical report describing that the use of controlled amounts of carbonate, acting both as complexing agent buffer led to a fairly satisfactory procedure for the determination of Th in Th-U alloys, using cupferron. The alloy, dissolved in NHO2, in the presence of HF, is treated with H2SO4 and the mixture is evaporated in SO2 fumes. The solution is diluted and (NH4)2CO2 is added. Th is precipitated from this solution with cupferron. The precipitate is weighed as ThO2 after ignition. An accuracy of 6% was obtained. A method was developed specifically for the determination of Th in U-Th alloys containing 1 to 10% Th. An ion exchange resin in column is used to separate Th from U, with NH2OH-HCl as complexing agent. The Th is then precipitated, ignited, and weighed in the conventional manner.

Abstract. A satisfactory method has been found for dissolving thorium metal and thorium oxide in heat-treated 25-12 stainless steel vessels without excessive corrosion of the vessels. The dissolution medium consists of strong HNO3 containing a small amount of fluoride or fluo-silicate. the fluoride required has no harmful effects on a subsequent solvent-extraction step for a separation of uranium isotopes from the dissolved thorium.

Abstract. A summary of the effect of metal, carbon, silicon, and oxygen impurities upon the various sulfide refractories is given and the proper procedures for elimination of the impurities are discussed. CeS which is properly prepared can be handled in air without danger of catching fire or appreciable oxidation. 650 satisfactory crucibles have been made to date using sulfides which were screened and pressed in air with less than 0.5% oxygen pickup. The other cerium and thorium sulfides are even more inert to oxidation than is CeS. Phase diagram possibilities are discussed for the cerium and thorium sulfide and oxy-sulfide systems. Further study of the ThS has shown that ThS crucibles are the highest melting and least volatile of the sulfide crucibles and ThS may be used for remelting of some metals up to 2000 degrees C. ThS crucibles appear to be the most suitable containers for metal reductions.

Abstract. The effect of various inhibitors on the production of CrIII in W waters containing chromatic has been studies at a variety of pH's in the CP-3 pile. The addition of 2 ppm NaClO3 appears to have little effect a a pH of 5.3, but 2 ppm NaClO3 cr 0.15 ppm of Cl2 (in the form of NaOCl) somewhat decreases the amount of chromatic reduced at a pH of 7.1. The inhibition is not great enough, however, to reduce the amount of CrIII formed to the maximum concentration permissible at W (0.02 ppm). The addition of 3 ppm (NH4)2S2O3 as an inhibiter will permit W water to be used a a Ph of 7.0, but not at a pH of 6.5 as far as chromate reduction is concerned. The concentration of CrIII would be 0.01 ppm and 0.05 ppm, respectively, after one passage through the pile. Previous conclusion as to the effects of temperature, pH, intensity and the addition of ammonium persulfate, which had been reached from experiments with simulation W water, have been checked by studies with solutions made from water chipped directly from Hanford. All of the effects noted were found to be similar to those already reported, …