Bismuth Solution Research Articles

Mutual interactions of thorium, lanthanides, and bismuth in Th-Ln-Bi solutions: Evidence for the formation of ThLnBi y compounds

The mutual solubilities of thorium and lanthanum, neodymium, or europium in bismuth solution have been determined over the temperature range 350–700 °C. Thorium and each lanthanide (Ln), dissolved in liquid bismuth, were found to interact to produce a solid compound with the apparent composition ThLnBi y. The variation of the mole fraction solubility products with temperature can be expressed as log K sp = log( N Th N Ln) = 2.410–6480/ T(K) for ThLaBi y and log K sp = 3.233–7285/ T(K) for ThNdBi y. The standard free energies of formation for ThLaBi y and ThNdBi y were estimated to be about (−114.8 + 0.0208 T) and (−99.8 + 0.0207 T) kcal/mole, respectively. The solubility of europium in bismuth was determined over the temperature range 350–550 °C. The data can be represented by the expression : log S Eu ( wt.%) = 4.4823-2973/ T(K).

Distribution of lanthanide and actinide elements between molten lithium halide salts and liquid bismuth solutions

Measurements of the equilibrium distribution of several lanthanide and actinide elements between liquid bismuth solutions and a variety of lithium halide salts were made in the temperature range 600–750°C. The salts included molten LiCl, LiBr and several LiFBeF 2ThF 4 solutions. At each temperature, the distribution coefficients (mole fraction in the bismuth phase divided by mole fraction in the salt phase) for most of the solutes obeyed the relationship D M = (N Li n) (K M ∗) , in which n is the oxidation number of solute M n+ in the salt phase and N Li is the mole fraction of lithium in the bismuth phase. Under the experimental conditions employed ( N Li ranging between 10 −5 and 0·3), thorium and protactinium were in the 4+ oxidation state in the salt phase; La, Nd, U, Np, Pu and Cm were tripositive; and Ba and Eu were dipositive. The values of log K M ∗ generally decreased regularly with increasing temperature. The oxidation numbers of Sm, Am and Cf in the salt phase varied between 3+ and 2+, depending on the experimental conditions. Californium existed primarily in the 2+ oxidation state with LiCl as the salt phase, whereas, in fluoride salts, the californium was tripositive. The variation of the distribution coefficients of Sm, Cf and Am with N Li at a given temperature could be expressed as D M = N Li 3/( α+ βN Li), in which α and β are constants.

Distribution of lanthanide and actinide elements between liquid bismuth and molten LiCl [sbnd]LiF and LiBr [sbnd]LiF solutions

The equilibrium distribution of several lanthanide and actinide elements between liquid bismuth solutions and molten LiCl LiF and LiBr LiF salt solutions was determined at 600 to 700°C with salt solutions in which the LiF concentration was varied from 0 to about 25 mole %. At a given temperature, the distribution coefficients ( D M ), which are defined as the concentration of M in the bismuth phase divided by the concentration of M in the salt phase, for each solute obeyed the relationship D M = (N Li n)(K M * ) with each salt solution used. In this expression, which is valid for a specific salt composition, N Li is the mole fraction of lithium in the bismuth phase, n is the oxidation number of M n+ in the salt phase, and K M * is a constant. At a given temperature, the variation of K M * with the LiF concentration in the salt phase could be expressed as log K M *=logK 0,M *−log [(1−N LiF) n + μ MN LiF nn] . In this expression, log K o,M * is the value of log K M * obtained with pure LiCl or LiBr as the salt phase and β M is a constant.

Correlation of the excess molar volumes of solutions of cadmium and bismuth in their molten halides

Correlation of the excess molar volumes of solutions of cadmium and bismuth in their molten halides

Bismuth-dithizone equilibria and hydrolysis of bismuth ion in aqueous solution

The reaction of bismuth with dithizone and the hydrolysis of bismuth ion in dilute solution were studied. Bismuth is extracted from aqueous solutions with carbon tetrachloride solutions of dithizone as the primary complex, Bi(HD z) 3 ; the molar absorptivities of dithizone and bismuth dithizonate have been determined. The extraction constant of the bismuth-dithizone system, K ext= [Bi(HD z) 3] o [H +] 3 /-[Bi 3+][H 2D z] o 3, has values of 8.2·10 10 and 5.8·10 10 at ionic strengths 0.1 and 1.0 respectively. The partition coefficient of bismuth dithizone, P Bi= [Bi(HD z) 3] o /-[Bi(HD z) 3] W, between carbon tetrachloride and water is 2.5·10 4 (μ=0.1). In dilute solution, bismuth ion hydrolysis results in the formation of the mononuclear species BiOH 2+...Bi(OH) 4 -. The cumulative formation constants for three of these species at 25° are: β 1=2.3·10 12 (μ=0.1), β 3=8.8·10 31 (μ=0.1), and β 4=7.9·10 32 (μ= variable), where β n= [Bi(OH) n 3- n ]/[Bi 3- n +][OH n ] n The formation of Bi(OH) + 2 was not studied. No evidence for the formation of polynuclear species in bismuth solutions ⩽10 -5 M was found.

Estimation of activity coefficients of barium and several lanthanide elements in liquid bismuth from distribution coefficient and thermochemical data

Measurements of the equilibrium distribution of barium and several lanthanides between liquid bismuth solutions and molten lithium halide salts yielded distribution coefficients that could be used in conjunction with published thermochemical data to estimate activity coefficients for the various elements (at low concentration) in liquid bismuth. The standard state for each element was the pure metal. At 600° C, the temperature at which most data were available, values of log γ M were about −12 for barium, −13 for lanthanum, −14 for cerium, −8 for neodymium, and −9 for gadolinium and dysprosium.

Estimated free energies of formation of PaCl 4, PaBr 4, and PaF 4, and activity coefficients for protactinium in liquid bismuth solutions

Estimated free energies of formation of PaCl 4, PaBr 4, and PaF 4, and activity coefficients for protactinium in liquid bismuth solutions

The elastic properties of magnesium solid solutions

The elastic moduli of quenched binary solid solutions of aluminum, bismuth, cadmium, indium, lead, lithium, silver, tin and zinc in magnesium have been measured and the results considered with reference to previous lattice parameter measurements. A simple variation with electron-atom ratio reveals no effects of Brillouin zone overlaps and earlier work invoking these is discussed in the light of the results. The decreasing modulus as the electron-atom ratio is increased may be explained in terms of a screening effect of the conduction electrons.

Chemistry and thermodynamics of the distribution of lanthanide and actinide elements between molten LiFBeF 2 and liquid bismuth solutions

Distribution coefficients (mole fraction in bismuth phase divided by mole fraction in salt phase) were determined for several lanthanide and actinide elements in molten LiFBeF 2-liquid bismuth systems. Most of the data were obtained at 600°C with LiFBeF 2 (66·7−33·3 mole %) as the salt phase, although some data were obtained in the temperature range 500–700°C and with LiFBeF 2 (56·9−43·1 mole %). At each temperature, the distribution coefficients ( D M ) obeyed the relationship D M = ( D Li n ) K′ M , in which n is the valence of the element in the salt phase. With the possible exceptions of samarium and americium, the valences of the various species were generally those expected. Samarium was divalent over the range of conditions studied. A significant fraction of the americium in the salt phase was found to be in the divalent state at 600°C. Values for log K′ U and log K′ Pu were obtained over the temperature range of 500–700°C. These values, when used in conjunction with other information from the literature, led to the following expressions for the free energies of formation of the respective trifluorides: ΔG UF3 f (kcal/mole) = −374·3 + 71·93( T/10 3), and + ΔG PuF3 f = −394·6 + 73·35( T/10 3).

Analytical applications of chelons: LVII. Chelometric determination of bismuth with DTPA and reciprocally

A new method is proposed for the chelometric determination of bismuth with DTPA using pyrocatechol violet as an indicator. The procedure has been used for determination 1 μg to 0.125 mg of bismuth, and is also useful for determination of DTPA with standard solution of bismuth.

Equilibrium distribution of actinide and lanthanide elements between molten fluoride salts and liquid bismuth solutions

The equilibrium distributions of several actinide and lanthanide elements between liquid bismuth solutions and a variety of LiF-containing molten fluoride salts were determined between 500 and 700°C. At each temperature, the distribution coefficients (mole fraction in bismuth phase divided by mole fraction in salt) obeyed the relationship D = ( D Li n ) K′, in which n is the valence of the element in the salt phase. Over the range of conditions investigated, Th, Pa, and Zr existed as tetravalent species in the salt; U, Np, Pu, Am, Cm, Cf, La, and Nd were trivalent; and, Eu was divalent. The distribution behavior of each element was affected by salt composition and temperature. Values of log K′ increased regularly with decreasing temperature. With LiFBeF 2ThF 4 (72-16-12 mole %) as the salt phase, the values of log K′ at 600°C for the trivalent actinide elements varied systematically with atomic number, and passed through a minimum near Z = 96(Cm).

Engineering Development of the MSBR Fuel Recycle

The molten-salt breeder reactor being developed at Oak Ridge National Laboratory (ORNL) requires continuous chemical processing of the fuel salt, 7LiF-BeF2-ThF4 (72-16-12 mole%) containing ~0.3 mole% 233UF4. The reactor and the processing plant are planned as an integral system. The main functions of the processing plant will be to isolate 233Pa from the neutron flux and to remove the rare-earth fission products. The processing method being developed involves the selective chemical reduction of the various components into liquid bismuth solutions at ~600°C, utilizing multistage counter-current extraction. Protactinium, which is easily separated from uranium, thorium, and the rare earths, would be trapped in the salt phase in a storage tank located between two extraction contactors and allowed to decay to 233U. Rare earths would be separated from thorium by a similar reductive extraction method; however, this operation will not be as simple as the protactinium isolation step because the rare-earth-thorium separation factors are only 1.3 to 3.5. The proposed process would employ electrolytic cells to simultaneously introduce reductant into the bismuth phase at the cathode and to return extracted materials to the salt phase at the anode. The practicability of the reductive extraction process depends on the successful development of salt-metal contactors, electrolytic cells, and suitable materials of construction.

Bismuth (V) Aqueous Fluoride Solution

WE wish to report the preparation and properties of moderately stable solutions of pentavalent bismuth in aqueous fluoride solutions. Apart from brief reports in two early papers1,2, the solution chemistry of Bi(V) has remained unexplored up to now.

An electromotive force study of solutions of bismuth in bismuth(III) chloride At 240°

Melts of BiCl 3 containing 0.2 to 20 mole % metal have been studied in sealed concentration cells without fixed reference at 240°. The marked nonideality required by the EMF data above about 1% Bi contrasts with the substantially ideal solutions of Bi + and Bi 3 + (vice Bi 4 4+) previously established at higher temperatures and lower metal concentrations. Combination of the EMF results with published cryoscopic data allows some limits to be placed on the activity coefficients of these species; in particular, positive deviation is required for the low-field Bi 3 + over much of the range. Other thermodynamic measurements on the concentrated solutions at higher temperatures are also considered briefly.

Dibutyl Carbitol Solvent Extraction of Polonium-210 from Nitric Acid Solutions of Irradiated Bismuth

Abstract: A continuous countercurrent solvent extraction process utilizing dibutyl carbitol as the extractant has been developed for separating 210Po from large amounts of associated bismuth. Both laboratory and pilot plant data demonstrate the process is a suitable headend step in recovery of kilogram quantities of 210Po. Typically, the extraction process recovers over 98% of the 210Po, essentially free from bismuth (Bi DF>1500), in a dilute HNO3 solution suitable as a starting material for final concentration and purification steps.

Determination of free acid in antimony(III) and bismuth(III) solutions

A method for the determination of free acid in antimony(III) and bismuth(III) solutions is given. A solution of the disodium salt of EDTA, 2–3 % in excess of the stoichiometric amount, is added to the metal salt solution and titrated with sodium hydroxide solution potentiometrically or visually using a mixed indicator. The error in the method is less than 0.5 %.

Development of Semiconductor Materials for Thermoelectric Cooling

ABSTRACTDevelopment of suitable materials for use in thermoelectric refrigeration is under progress. In this process the electrical resistivity and the seebeck coefficient of the solid solutions Bi2Te3 (80 per cent)+Bi2Se3 (20 per cent) and Bi2Te3 (26 per cent) + Sb2Te3 (74 per cent) as functions of AgI doping and of excess tellurium respectively have been studied.It is concluded that the bismuth telluride-bismuth selenide solid solution with 0·2 per cent AgI doping gives the best result as a n-type leg for thermoelectric refrigeration. The bismuth telluride antimony telluride solid solution with 4 per cent excess weight of tellurium is found to give the best results for the p-type leg. The best values for (α2σ) found is 30·6 × 10−4 V/ohm cm.°C. for the n-type and 58·1 × 10−4 V/ohm cm.°C. for the p-type. Some experiments on the contact resistance between the semiconductor and a copper plate have also been made.

Densities of Liquid Solutions of Bismuth and Sulfur1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDensities of Liquid Solutions of Bismuth and Sulfur1Daniel CubicciottiCite this: J. Phys. Chem. 1964, 68, 3, 537–540Publication Date (Print):March 1, 1964Publication History Published online1 May 2002Published inissue 1 March 1964https://doi.org/10.1021/j100785a016RIGHTS & PERMISSIONSArticle Views45Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (372 KB) Get e-Alerts

Ni, CuのCu-Bi, Ni-Bi溶液への溶解現象

Ni, CuのCu-Bi, Ni-Bi溶液への溶解現象

Photometric titrations—V : A selective, chelometric determination of cobalt

Cobalt can be titrated with good selectivity by converting it with hydrogen peroxide in alkaline medium to the cobalt III EDTA complex and back-titrating photometrically in acid medium the excess EDTA with bismuth solution, using pyrocatechol violet as indicator. No interference is observed with alkalies, alkaline earths, Ni, Cu, Cd, Zn, Pb, Al, U, and W. Bi, Zr, In, Ga and other ions forming very stable EDTA complexes are co-titrated. Mo, Fe, Ag and Hg interfere and should be separated. The interference of Mn can be excluded by addition of ascorbic acid. Th can be masked with sulphate. Cr III is co-titrated, but by applying a difference method operating with two aliquots, both Cr and Co can be determined. Complexing anions interfere, as does chloride, which causes a turbidity with bismuth.