Formation of MPd (M = Gd, Np) by the reaction of MN with Pd and chlorination of MPd using cadmium chloride

Hayashi, Hirokazu; Shibata, Hiroki; Sato, Takumi; Otobe, Haruyoshi

Journal of Radioanalytical and Nuclear Chemistry, 332(2), p.503 - 510, 2023/02

https://doi.org/10.1007/s10967-023-08760-4

The formation of MPd (M = Gd, Np) by the reaction of MN with Pd at 1323 K in Ar gas flow was observed. Cubic AuCu-type GdPd ( = 0.4081 0.0001 nm) and NpPd ( = 0.4081 0.0001 nm) were identified, respectively. The product obtained from the reaction of NpN with Pd contained additional phases including the hexagonal TiNi-type NpPd. Chlorination of the MPd (M = Gd, Np) samples was accomplished by the solid-state reaction using cadmium chloride at 673 K in a dynamic vacuum. Pd-rich solid solution phase saturated with Cd and an intermetallic compound PdCd were obtained as by-products of MCl formation.

Density functional theory study on the Ir Mssbauer spectroscopic parameters of Vaska's complexes and their oxidative adducts

Kaneko, Masashi; Nakashima, Satoru*

Inorganic Chemistry, 60(17), p.12740 - 12752, 2021/09

https://doi.org/10.1021/acs.inorgchem.1c00239

In the present study, density functional theory (DFT) calculation was applied to Vaska's complexes of formula -[IrCl(CO)(PPh)], and their oxidative adducts with small molecules (YZ) including H, i.e., -[IrCl(YZ)(CO))(PPh)], to successfully correlate the electronic states of the complexes with the corresponding Ir Mssbauer spectroscopic parameters. After confirming the reproducibility of the DFT methods for elucidating the equilibrium structures and Ir Mssbauer isomer shifts of the octahedral Ir complexes, the isomer shifts and quadrupole splitting values of Vaska's complexes and their oxidative adducts were calculated. A bond critical point analysis revealed that the tendency in the isomer shifts was correlated with the strength of the covalent interaction in the coordination bonds. In an electric field gradient (EFG) analysis of the oxidative adducts, the sign of the principal axis was found to be positive for the complex with YZ = Cl and negative for the complex with YZ = H. This reversal of the sign of the EFG principal axis was caused by the difference in the electron density distribution for the coordination bonds between Ir and YZ, according to a density of states analysis.

Development of separation technique for platinum group metals from radioactive liquid waste utilizing laser-induced particulate formation

Saeki, Morihisa*; Asai, Shiho; Oba, Hironori*

Bunseki, 2018(4), p.138 - 143, 2018/04

Platinum group metal (PGM) has attracted much attention in light of increasing demands in the industrial sector. A wide variety of techniques specialized for PGM separation, such as, solvent extraction, solid phase extraction, and molten salt electrolysis have been developed so far. Among such techniques, a newly developed separation technique based on laser-induced particulate formation can be a promising alternative to conventional ones. It enables non-contact and highly-selective separation with a simple operation. In this review, the research history and the basic mechanism of laser-induced particulate formation were outlined. Several applications were also mentioned, focusing on our latest research progress which achieved a world first quantitation of radioactive palladium in a spent nuclear fuel sample.

Chemical state analysis of rhodium in simulated waste glass by synchrotron-radiation-based XAFS and imaging XAFS techniques

Okamoto, Yoshihiro; Nagai, Takayuki; Shiwaku, Hideaki; Inose, Takehiko*; Sato, Seiichi*

Nihon Genshiryoku Gakkai Wabun Rombunshi, 16(4), p.180 - 190, 2017/12

https://doi.org/10.3327/taesj.J16.024

X-ray absorption fine structure (XAFS) and imaging XAFS analyses were performed to elucidate chemical state of rhodium in the simulated waste glass. The chemical forms of Rh in the glass were evaluated to be 84% RhO and 16% metal/alloy as the result of linear combination analysis of EXAFS data. According to the imaging XAFS analysis, the chemical form of Rh which was located together with Ru was mainly oxide (RhO). It suggests that stable (Ru,Rh)O solid solution exists in the simulated glass. On the other hand, that of Rh of which distribution did not accord with Ru in the glass was mainly metallic. In the case of metallic Rh in the glass, it tended to become an aggregation form. It can be concluded that the chemical state of Rh was much affected by the existence and distribution of Ru element.

Cold and semi-hot tests of 4-group partitioning process at NUCEF

Morita, Yasuji; Yamaguchi, Isoo; Fujiwara, Takeshi; Mizoguchi, Kenichi*; Kubota, Masumitsu*

JAERI-Research 2000-024, 55 Pages, 2000/06

JAERI-Research-2000-024.pdf:2.24MB

no abstracts in English

The ninth test run of Joule-Heated cylindrical electrode melter on an engineering scale (JCEM-E9); Research report on solidification of high-level liquid waste

; ; *; *; Masaki, Toshio; Kobayashi, Hiroaki; *

PNC TN8410 98-041, 185 Pages, 1998/02

PNC-TN8410-98-041.pdf:7.51MB

The 9 test of Joule-Heated Cylindrical Electrode Melter - Engineering Scale (JCEM-E9 Test) was carried out from June to July 1996, as a part of the development program on an advanced glass melter. The principal purpose of the test was to estimate the effect of noble metal on operation of the melter with simulated high-level liquid waste. Besides, we also evaluated the basic operational characteristics with corrosion of electrodes, qualities of produced glass etc. JCEM-E is an electric glass melter with an internal electrode and an external electrode in a subsidiary furnace. The internal electrode is a rod inserted in the center of external electrode that is a cylindrical tank. The glass is melted by conducting electric current through the molten glass between the internal and external electrodes. The subsidiary furnace is composed of multi-layer refractories inside a metallic casing and is equipped with the resistance heaters. Melting surface area is 0.35 m that i8 approximately half of 0.66 m of TVF melter. In the test, 13 batches of glass was produced and total weight of produced glass was 3663kg. As a result, The maximum processing rate of JCEM-E with simulated HLLW including noble metals was 4.205.60kg/h, and decreased to less than 80 percent compared with JCEM-E8 Test with non-noble metals HLLW. It was considered that the decrease of the rate arose from concentration of current due to non-uniform distribution of noble metals in molten glass. Judging from the balance of feed and draining, and as a consequence of the observation inside the melter after the test, the draining of noble metals from the nozzle was good. As for the quality of glass produced in the test, properties of concern were comparable with those of standard glass of TVF.

None

Myochin, Munetaka; Iwase, Masanori*

PNC TY8604 96-001, 32 Pages, 1996/03

PNC-TY8604-96-001.pdf:1.24MB

no abstracts in English

Wet partitioning and waste treatment

Morita, Yasuji; Kubota, Masumitsu

Hoshasei Haikibutsu Kenkyu, 2(1-2), p.75 - 83, 1996/02

no abstracts in English

None

Sasage, Kenichi; ; Ouchi, Jin

PNC TN8100 94-003, 337 Pages, 1994/02

PNC-TN8100-94-003.pdf:11.55MB

no abstracts in English

None

Kawamura, Kazuhiro; ;

PNC TN8600 93-003, 269 Pages, 1993/02

PNC-TN8600-93-003.pdf:8.79MB

no abstracts in English