Standard Gibbs energy of formation of Cs2CdI4

The vapor pressures of CdI₂ and Cs₂CdI₄ were measured below and above their melting points, employing the transpiration technique. The standard Gibbs energy of formation Δ_fG° of Cs₂CdI₄, derived from the partial pressure of CdI₂ in the vapor phase above and below the melting point of the compound could be represented by the equations Δ_fG°Cs₂CdI₄ (±6.7) kJ mol⁻¹=−1026.9+0.270 T (643 K≤T≤693 K) and Δ_fG°{Cs₂CdI₄} (±6.6) kJ mol⁻¹=−1001.8+0.233 T (713 K≤T≤749 K) respectively. The enthalpy of fusion of the title compound derived from these equations was found to be 25.1±10.0 kJ mol⁻¹ compared to 36.7 kJ mol⁻¹ reported in the literature from differential scanning calorimetry (DSC). The standard enthalpy of formation Δ_fH°_298.15 for Cs₂CdI₄ evaluated from these measurements was found to be −918.0±11.7 kJ mol⁻¹, in good agreement with the values −920.3±1.4 and −917.7±1.5 kJ mol⁻¹ reported in the literature from two independent calorimetric studies.     

Thermodynamic studies on Cs4U5O17(s) and Cs2U2O7(s) by emf and calorimetric measurements

The oxygen potentials over the phase field: Cs₄U₅O₁₇(s)+Cs₂U₂O₇(s)+Cs₂U₄O₁₂(s) was determined by measuring the emf values between 1048 and 1206 K using a solid oxide electrolyte galvanic cell. The oxygen potential existing over the phase field for a given temperature can be represented by: Δμ(O₂) (kJ/mol) (±0.5)=−272.0+0.207T (K). The differential thermal analysis showed that Cs₄U₅O₁₇(s) is stable in air up to 1273 K. The molar Gibbs energy formation of Cs₄U₅O₁₇(s) was calculated from the above oxygen potentials and can be given by, Δ_fG⁰ (kJ/mol)±6=−7729+1.681T (K). The enthalpy measurements on Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were carried out from 368.3 to 905 K and 430 to 852 K respectively, using a high temperature Calvet calorimeter. The enthalpy increments, (H⁰_T−H⁰₂₉₈), in J/mol for Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) can be represented by, H⁰_T−H⁰_298.15 (Cs₄U₅O₁₇) kJ/mol±0.9=−188.221+0.518T (K)+0.433×10⁻³T² (K)−2.052×10⁻⁵T³ (K) (368 to 905 K) and H⁰_T−H⁰_298.15 (Cs₂U₂O₇) kJ/mol±0.5=−164.210+0.390T (K)+0.104×10⁻⁴T² (K)+0.140×10⁵(1/T (K)) (411 to 860 K). The thermal properties of Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were derived from the experimental values. The enthalpy of formation of (Cs₄U₅O₁₇, s) at 298.15 K was calculated by the second law method and is: Δ_fH⁰_298.15=−7645.0±4.2 kJ/mol.     

Enthalpies of formation of U-, Th-, Ce-brannerite: implications for plutonium immobilization

Brannerite, ideally MTi₂O₆, (M=actinides, lanthanides and Ca) occurs in titanate-based ceramics proposed for the immobilization of plutonium. Standard enthalpies of formation, ΔH⁰_f at 298 K, for three brannerite compositions (kJ/mol): CeTi₂O₆ (−2948.8 ± 4.3), U_0.97Ti_2.03O₆ (−2977.9 ± 3.5) and ThTi₂O₆ (−3096.5 ± 4.3) were determined by high temperature oxide melt drop solution calorimetry at 975 K using 3Na₂O · 4MoO₃ solvent. The enthalpies of formation were also calculated from an oxide phase assemblage (ΔH⁰_f-ox at 298 K): MO₂ + 2TiO₂=MTi₂O₆. Only UTi₂O₆ is energetically stable with respect to an oxide assemblage: U_0.97Ti_2.03O₆ (ΔH⁰_f-ox=−7.7±2.8 kJ/mol). Both CeTi₂O₆ and ThTi₂O₆ are higher in enthalpy with respect to their oxide assemblages with (ΔH⁰_f-ox=+29.4±3.6 kJ/mol) and (ΔH⁰_f-ox=+19.4±1.6 kJ/mol) respectively. Thus, Ce- and Th-brannerite are entropy stabilized and are thermodynamically stable only at high temperature.     

Standard Gibbs energy of formation of Mo3Te4 by emf measurements

The emf of the galvanic cells Pt, Mo, MoO₂¦8 YSZ¦‘FeO’, Fe, Pt (I) and Pt, Fe,‘FeO’ ¦8 YSZ¦MoO₂, Mo₃Te₄, MoTe₂(), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo₃Te₄/MoTe₂(), was found to be

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. Using the literature data for the Gibbs energy of formation of MoTe₂(). the expression ΔG°_f(Mo₃Te_4,s) ± 5.97 (kj/mol) = −253.58 + 0.09214T(K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of −209 ± 10 kJ/mol for ΔH°_f.298^o of Mo₃Te₄(s).     

The constitution of the uranium-tin-palladium system

The Pd-rich region of the isothermal section of the ternary U---Sn---Pd system at 1050°C was investigated by metallography, X-ray microanalysis and X-ray diffraction. The fcc -Pd(Sn, U) solid solution dissolves up to 16 at.% Sn and 15 at.% U. The AuCu₃ type phases SnPd₃ and UPd₄ are the end members of a single-phase region. SnPd₂ and UPd₃ are in equilibrium with this solid solution of the composition U_0.68Sn_0.32Pd₃ and with the ternary phase USnPd₂. The Gibbs energies of formation of SnPd₂, SnPd₃ and UPd₄ were used and ideal behaviour of the (Sn, U) Pd_3+x solid solution was assumed to calculate the Gibbs energy of formation of UPd₃ which gives Δ_fG° = −312 kJ/mol at 1050°C. In addition, the annealing experiments in the Pd-rich region of the binary U---Pd system were extended to 950°C which confirm the phase-field distribution established at 1050°C in earlier work.     

Thermodynamic stability of Na2ZrO3 using the solid electrolyte galvanic cell technique

The sodium potential in the test electrode (a) Pt,O₂,Na₂ZrO₃,ZrO₂ was measured by using the emf technique employing Na-β^″-alumina as the solid electrolyte in conjunction with (b) Pt,O₂,Al₂O₃,NaAl₁₁O₁₇, (c) Pt,O₂,Na₂MoO₄,Na₂Mo₂O₇ and (d) Pt,Na₂CO₃,CO₂,O₂ as the reference electrodes over the ranges 880–1045, 700–800 and 850–940 K, respectively. The emf results between electrodes (b) and (c) were utilized for internal consistency checks. From the results on cells formed between (a) and (b) and those on (a) and (c), the standard Gibbs energy of formation, Δ_fG^o (kJ/mol) of Na₂ZrO₃ was determined to be −1699.4+0.3652T (K) valid over the temperature range 700–1045 K. The break in the emf data at 1045 K was corroborated by independent TG/DTA measurements carried out on Na₂ZrO₃ which exhibited an endotherm at 1055 K indicative of a phase transition in Na₂ZrO₃.     

Enthalpy and heat capacity of LiAlO2 between 298 and 1700 K by drop calorimetry

The enthalpy of γ-LiAlO₂ was measured between 403 and 1673 K by isothermal drop calorimetry. The smoothed enthalpy curve between 298 and 1700 K results in H⁰(T) − H⁰(298 K)=−37 396 + 93.143 · T + 0.00557 · T² + 2 725 221 · T⁻¹ J/mol. The standard deviation is 2.2%. The heat capacity was derived by differentiation of the enthalpy curve. The value extrapolated to 298 K is C_p,298=(65.8 ± 2.0) J/K mol.     

Interface mixing induced by swift heavy ions at metal-oxide/silicon interfaces

It was observed previously that ceramic/ceramic bilayers were very sensitive with respect to the electronic stopping power S_e, i.e. strong interface mixing, scaling with , occurred if a threshold S_ec was exceeded. The threshold seemed to be determined by the higher track formation threshold of two constituents forming the bilayer. Although no track formation has been observed in crystalline Si even for Uranium projectiles, interface mixing was observed previously for some Si-multilayers.

In this paper we report on the interface mixing of NiO, Fe₂O₃, TiO₂ on Si due to irradiation with 90–350 MeV Ar-, Kr-, Xe- and Au-ions at 80 K at fluences up to 9E15 ions/cm². Interface mixing, analyzed by means of Rutherford Backscattering Spectrometry (RBS), is found for these bilayers, too. But the threshold for intermixing is significantly higher compared to the ceramic/ceramic bilayers. This observation could be an evidence for the threshold being determined by the Si-layer. In contrast to NiO/Si and Fe₂O₃/Si, where an usual random walk mixing Δσ² = kΦ was observed, the interface broadening Δσ² for TiO₂/Si is found to scale nonlinearly with the ion fluence, which indicates that mixing is driven by a chemical solid-state reaction. At higher fluences plateaus form at the low energy Ni-edge of the RBS spectra. The plateaus indicate phase formation. X-Ray diffraction spectra does not show any evidence for new crystalline phases.     

Thermochemical study of vaporization of LiTiO by a mass spectrometric Knudsen effusion method

The vaporization of Li₄TiO₄ has been studied by a mass spectrometric Knudsen effusion method in the temperature range 1082–1582 K. Identified vapors are Li(g), LiO(g), Li₂O(g) and Li₃O(g). When the vaporization proceeds, the content of Li₂O in the Li₄TiO₄ sample decreases and the condensed phase of the sample changes to β-Li₄TiO₄ plus l-Li₂TiO₃ below 1323 K, to β-Li₄TiO₄ plus h-Li₂TiO₃ in the range 1323–1473 K and to h-Li₂TiO₃ plus liquid above 1473 K. On the basis of the partial pressure data, the enthalpies of formation for β-Li₄TiO₄ from elements and from constituent oxides have been determined to be ΔH_f,298^°(β-Li₄TiO₄,s) = −2247.8 ± 14.3 kJ mol⁻¹ and Δ_fox,298^°(β-Li₄TiO₄, s) = −107.3 ± 14.3 kJ mol⁻¹, respectively.     

Chemical thermodynamic representation of AmO2−x

The AmO_2−x solid solution data set for the dependence of the oxygen potential on the composition, x, and temperature was retrieved from the literature and represented by a thermodynamic model. The data set was analysed by least-squares using equations derived from the classical thermodynamic theory for the solid solution of a solute in a solvent. Two representations of the AmO_2−x data were used, namely the Am_5/4O₂–AmO₂ and AmO_3/2–AmO₂ solid solution. No significant difference was found between the two, and the Am_5/4O₂–AmO₂ solution was preferred on the basis of the phase diagram. From the results the Gibbs energy of formation of Am_5/4O₂ has been derived.     

The thermal conductivity of UO2 vapor

The thermal conductivity, λ of a saturated vapor over UO_1.96 is calculated in the temperature range 3000–6000 K. The calculation shows that the contribution to λ from the transport of reaction enthalpy dominates all other contributions. All possible reactions of the gaseous species UO₃, UO₂, UO, U, O, and O₂ are included in the calculation. We fit the total thermal conductivity to the empirical equation λ = exp(a+ b/T+cT+dT² + eT³), with λ in cal/(cm s K), T in kelvins, a = 268.90, B = − 3.1919 × 10⁵, C = −8.9673 × 10⁻², d = 1.2861 × 10⁻⁵, and E = −6.7917 × 10⁻¹⁰.     

Role of nuclear energy in environment, economy, and energy issues of the 21st century – Growing energy demand in Asia and role of nuclear

The economic growth of recent Asia is rapid, and the GDP and the energy consumption growth rate are about 8–10% in China and India. The energy consumption forecast of Asia in this century was estimated based on the GDP growth rate by Goldman Sachs. As a result, about twice in India and Association of South East Asian Nations (ASEAN) and about 1.5 times in China of SRES B (Special Report on Emission Scenarios) are forecasted. The simulation was done by Grape Code to analyze the impact of energy increase in Asia. As for the nuclear plant in Asia, it is expected 1500 GWe in 2050 and 2000 GWe in 2100, in the case of the environmental constrain. To achieve this nuclear utilization, there are two important aspects, technically and institutionally.

A. Development of the CANDLE core and/or the Breed and Burn core.

B. The establishment of the stable nuclear fuel supply system like “Asian nuclear fuel supply organization”.

The diffusivities of fission-created or thermally-doped tritium in UO2

The diffusion behavior of tritium in UO₂ was studied. Two methods were adopted for the introduction of tntium into UO₂: one via ternary fission of ²³⁵U and the other via thermal doping. In the former, the diffusion constants decreased with increase in sample weight. The diffusion constants obtained from the pellet with the same specification (9 mm in diameter, 5 mm high) were D″_bulk = 3.03 × 10⁻³(^+0.369_−0.003) exp[−163±43(kJ/mol)/RT](cm²/s) for fission-created tritium and D′_bulk = 0.15(^{+ 0.94}_−0.13) exp[−76±13 (kJ/mol)/RT](cm²/s) for thermally-doped tritium. The difference of the diffusion constants between two systems was discussed in terms of the effects associated with the recoil processes of energetic tritium.     

Structure and kinetic studies of U(VI)-benzamidoxime complex in non-aqueous solutions by H- and C-NMR

The structural and kinetic studies of U(VI) complex with benzamidoxime(Hba) as ligand in CD₃COCD₃ have been studied by means of ¹H and ¹³C NMR. The Hba molecule was found to coordinate to UO₂²⁺ in the form of anionic benzamidoximate (ba), and the number of ba coordinated to UO₂²⁺ was determined to be 3 by analyzing the chemical shift of ¹³C NMR signal for Hba in the presence of UO₂²⁺. The exchange rate constants(k_ex) of ba in [UO₂(ba)₃] were determined by the NMR line-broadening method. The kinetic parameters were obtained as follows: k_ex(25°C) = 3.1 × 10³s⁻¹, ΔH^≠ = 35.8 ± 3.5 KJ mol⁻¹, and ΔS^≠ = −65 ± 13.7 J K⁻¹ mol⁻¹. The UV-visible absorption spectra of solutions containing UO₂²⁺ and Hba were also measured. The molar extinction coefficient of the complex was found to be extremely large compared with those of UO₂(L)₅²⁺ (L = unidentate oxygen donor ligands) complexes. This is due to the strong electron withdrawing of UO₂²⁺ from Hba and suggests that an interaction between UO₂²⁺ and Hba is very strong. Such a high affinity of monomeric amidoxime to UO₂²⁺ reasonably explains the high adsorptibility of amidoxime resin to U(VI) species, and is considered to result in the high recovery of U(VI) species from sea water using amidoxime resin.     

The kinetics and mechanism of the uranium-water vapour reaction — an evaluation of some published work

The published results of Grimes and Morris on the rate of the uranium-water vapour reaction which were obtained using interferometry have been recalculated using the best values derived from the literature for the complex refractive indices of uranium and uranium dioxide (3.1–3.91 for uranium and 2.2-0.51 for uranium dioxide). The kinetics have been described by Haycock's model and the linear rate constant is given by K₁ = 1.3 × 10⁴P^1/2_H2O exp( − 9.0 kcal/RT )mg U/cm² h, where P_H2O is the water vapour pressure in torr or K₁ = 3.48 × 10⁸r^1/2 exp( −14.1 kcal/RT)mg U/cm² h, where r is the fractional relative humidity, R is the gas constant and T is the absolute temperature.

A mechanism is described which accounts for the observed dependence of the rate of uranium-water vapour reaction on the square root of the water vapour pressure.     

Diamagnetic measurement on HT-7 superconducting tokamak

Diamagnetic measurement is a basic diagnostics on tokamak. Some important plasma parameters such as plasma energy and betap β_p can be obtained from this measurement. For most case, diamagnetic flux ΔΦ is extremely smaller than toroidal flux Φ (ΔΦ/Φ − 10⁻⁴). Therefore we have to use techniques that allow measurement to better than 1 part in 104 to get 10% accuracy in value of β_p. Using a compensation coil is a typical technique to improve the signal to noise ratio. In this paper the design of diamagnetic diagnostics system for HT-7 superconducting tokamak device is introduced and some experimental results of plasma energy and β_p are given in different plasma discharges.     

Resonant coherent excitation of 2s electron of Li-like Fe ions to the n = 3 states

We observed resonant coherent excitation of the 2s electron to the n = 3 states of 83.5 MeV/u Li-like Fe²³⁺ ions planar-channeling in the plane of a Si crystal. A survival fraction of the Li-like ions was measured as a function of the angle between the incident beam and the [0 0 1] axis. Clear resonance dips corresponding to the transitions of a 2s electron to all the n = 3 states were observed. The transition of each resonance dip was identified by comparing with spectroscopic data. The resonance dips at the transition energies corresponding to the optically forbidden 2s_1/2–3s_1/2, 2s_1/2–3d_3/2 and 2s_1/2–3d_5/2 transitions were observed as well as the resonance dips at transition energies corresponding to the optically allowed 2s_1/2–3p_1/2 and 2s_1/2–3p_3/2 transitions.     

Investigation of metal matrix systems for cosmogenic Al analysis by accelerator mass spectrometry

We report experiments designed to help optimize accelerator mass spectrometry (AMS) of ²⁶Al (in the form of Al₂O₃) for geochronologic and geomorphologic applications. Analysis times are long and the precision of AMS are restricted by counting statistics for ²⁶Al, which are in turn limited by the intensity of Al⁻ beam currents. We show that ion beam currents are affected by the metal matrix in which Al₂O₃ is dispersed, by the matrix-to-Al₂O₃ mixing ratio, and for at least some matrices, such as Ag, by the depth to which the sample is packed in the AMS cathode. Typical instantaneous Al⁺⁷ currents (μA) produced by the LLNL CAMS Cs sputter ion source and measured in a Faraday cup after the accelerator are 2.26 for samples in Ag, 2.17 in Re, 2.00 in Nb, 1.92 in V and 1.73 in Mo. The AMS counting efficiency (Al⁻ ions detected per Al atom loaded in the target) for a constant analysis time (900 s) and for equimolar mixtures of Al₂O₃ and matrix is in the range of 6 × 10⁻⁵–9 × 10⁻⁵ in the order Ag > Re > Nb > V > Mo. Additionally, we observed a correlation between the ion detection efficiency (Al ions detected per Al atoms loaded) and the matrix work function and inverse vaporization enthalpy of the matrix and beam current. Typical currents (μA) obtained with elemental Al are 13.3 for samples in no matrix, 3.23 in V, 3.14 in Nb, 3.07 in Re, 2.85 in Mo, 1.46 in Ag. The ion detection efficiency for elemental Al correlates strongly with matrix electron affinity. Thus, our data indicate that the current practice of mixing Al₂O₃ with Ag is reasonable until a means is found to produce cathodes of elemental Al.     

Threshold oxygen levels in sodium necessary for the formation of NaCrO2 in sodium-steel systems

A knowledge of the threshold oxygen level in liquid sodium necessary for the formation of NaCrO₂ in sodium-steel systems is useful in the operation of fast breeder reactors. There is considerable discrepancy in the data reported in the literature. In order to resolve this, the problem was approached from two sides. Direct measurement of oxygen potential in the Na(l)-Cr(s)-NaCrO₂(s) phase field using the galvanic cell In, In₂O₃/YDT/Na, Cr, NaCrO₂ yielded: _o2 = −800847 + 147.85 T J/mol O₂ (657–825 K). Knudsen cell-mass spectrometric measurements were carried out in the phase field NaCrO₂(s)-Cr₂O₃(s)-Cr(s) to obtain the Gibbs energy of formation of NaCrO₂ as: ΔG^o_f,T(NaCrO₂) = −870773 + 193.171 T J/mol (825–1025 K). The threshold oxygen levels deduced from G^o_f,T (NaCrO₂) data were an order of magnitude lower than the directly measured values. The difference between the two sets of data as well as differing experimental observations from operating liquid sodium systems are explained on the basis of the influence of dissolved carbon.     

Elastic recoil detection analysis on the ANSTO heavy ion microprobe

The heavy ion microprobe at the Australian Nuclear Science and Technology Organisation is capable of focussing heavy ions with an ME/q² of up to 100 amu MeV. This makes the microprobe ideally suited for heavy ion elastic recoil detection analysis (ERDA). However, beam currents on a microprobe are usually very small, which requires a detection system with a large solid angle. We apply microbeam heavy ion ERDA using a large solid angle ΔE−E telescope with a gas ΔE detector to layered structures. We demonstrate the capability to measure oxygen and carbon with a lateral resolution of 20 μm, together with determination of the depth of the contamination in thin deposited layers.