Absorption Spectra of the Lanthanides in Fused Lithium Chloride-Potassium Chloride Eutectic

Banks, Charles V.; Heusinkveld, Merlyn R.; O'Laughlin, Jerome W.

doi:10.1021/ac60177a032

Cited by 51 publications

(32 citation statements)

References 30 publications

(16 reference statements)

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“…The spectrum resembles previous measurements at 400 "C except for the absence of two bands given by Banks et al (3). Table ID3 summarizes the band positions and assignments for several hosts.…”

Section: Praseodymiumsupporting

confidence: 71%

Solvent LiCl–KCl in the nephelauxetic series for trivalent rare earths

Johnson¹,

Sandoe²

1968

Can. J. Chem.

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The spectra of trivalent Ce, Pr, Nd, Sm, Eu, Tb, Dy, Tm, and Yb ions in molten LiCI-KC1 at 450 "C are reported over the range 0.28 to 2.8 ~r, and the baricenters of terms are tabulated for a wide variety of crystal and liquid hosts. These hosts can be arranged in a nephelauxetic series and for Pr3+ actual nephelauxetic parameters, (3, can be calculated by comparing average multiplet energies.Canadian Journal of Chemistry, 46, 3457 (1968) The region of optical transparency for fused salt media can extend quite far into the infrared. For instance, the limiting wavelengths are 2.6 p for LiN03-KNO, eutectic at 150 "C (I), 2.8 p for LiC1-KC1 eutectic at 450 "C (2), and 2.7. p for a ternary sulfate at 550 "C compared with 1.4 p for water at 25 "C. This is useful for the study of lanthanide ions since their 4f" bands in this region are less subject to the complications of overlapping multiplets. Pm3+ in LiC1-KC1 eutectic at 400 "C through the visible and near infrared regions to 1 p. Sm3+ and Pr3+ ions have been investigated in LiC1-KC1 eutectic with high resolution in the near infrared (2), while several ions were studied in LiCl-KC1-NaCI eutectic at 400 "C (4). Carnall and co-workers (5-7) discussed the spectra of all the trivalent lanthanides except La3 + and Ce3 + in LiN0,-KN03 eutectic in terms of the transitions between LS multiplets of 4f". Certain ions were studied from an analytical viewpoint in fluoride melts by Young and White (8,9) and the spectrum of Nd3+ in LiCl-KC1 and LiF was used to illustrate the use of the Unicam S.P. 700 spectrophotometer (10). The characteristic narrow bands of these ions appeared in all melts but some fine structure was lost. Bands obtained only in nitrate melts in the 1.7 p region were ascribed to water contamination (4). A temperature increase of 400 "C caused a bathochromic shift of the Ho3 + bands (4) but a 200 "C increase showed no effect on the Nd3+ bands (10). This paper reports the spectra of several trivalent lanthanides in LiCl-KC1 eutectic a t 450 "C over the range 0.28 to 2.8 p. Comparisons are made with the spectra in other solvents and crystals and actual or relative nephelauxetic parameters are evaluated for the 4f electrons. A discussion of the nephelauxetic effect in rare earths appears in Sinha's book (11) together with other tables of spectra. Experimental Preparation of Lauthanide Ion Sol~~tior~s in LiCI-KC1E~rtectic Pure anhydrous eutectic was prepared by a procedure essentially following Laitinen, Tischer, and R o e (12). SmCI, was prepared by passing HCI over hydrated chloride (Johnson Matthey Ltd., London) in a silica boat while raising the temperature to 550 "C over a period of 30 h. YbCI, was purified by sublin~ation of so-called anhydrous material (Koch Light Laboratories) a t 600 OC, 5 x r on to a water-cooled finger; the raw material was 3 % deficient in chlorine and gave turbid solutions in the melt. Thcse two salts could be added directly to the solvent. The hydrated chloride or oxides of the other ions (Johnson Matthey Ltd., Koch Light) were adde...

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Section: Praseodymiumsupporting

confidence: 71%

Solvent LiCl–KCl in the nephelauxetic series for trivalent rare earths

Johnson¹,

Sandoe²

1968

Can. J. Chem.

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“…Adding LiCl into CsCl resulted in the distortion of the symmetry. The octahedral symmetry of NdCl 6 3− was also found to be distorted with increasing temperature. These observations should be useful for understanding the thermochemical stabilities of f-elements in melts, which greatly influence the performance of the reprocessing process.…”

Section: Introductionmentioning

confidence: 93%

“…To enhance the basic knowledge for the pyrochemical reprocessing, we investigate the behavior of trivalent f-elements in molten salts with this analytical technique. We have focused on the hypersensitive transition of neodymium, and studied the structural property of the NdCl 6 3− complex in various molten chlorides [1]. The highly symmetric octahedral coordination has been confirmed in the NaCl-2CsCl eutectic and in the CsCl.…”

Section: Introductionmentioning

confidence: 99%

Electronic absorption spectra of lanthanides in a molten chloride

Fujii

Nagai

Uehara

et al. 2007

Journal of Alloys and Compounds

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“…[13], and 10 Lmol −1 cm −1 for molten Cs 2 NaNdCl 6 at 973 K [13]. Other peaks have been also reported in [12,13], and their intensities are proportional to the concentration of NdCl 3 , as shown in Figure 1.…”

Section: Uv/visible Spectrophotometrymentioning

confidence: 58%

Spectrophotometric Study of Nd²⁺ Ions in LiCl-KCl Eutectic Melt

Hayashi

Akabori

Ogawa

et al. 2004

Zeitschrift Für Naturforschung A

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A UV and visible spectrophotometric study was made in order to prove the existence of Nd 2+ and clarify the equilibrium among Nd metal, Nd 2+ , and Nd 3+ in LiCl-KCl eutectic melt. Spectra assigned to Nd 2+ were observed for NdCl 2 in (LiCl-KCl) eut. and Nd-NdCl 3 in (LiCl-KCl) eut. melts. Black corrosion products were observed on the surface of the glass cells used for the measurements, where the spectra assigned to Nd 2+ were observed. X-ray diffraction measurements and electron-probe micro-analyses of the corroded glass cells revealed that the corrosion products contained NdOCl.

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Absorption Spectra of the Lanthanides in Fused Lithium Chloride-Potassium Chloride Eutectic

Cited by 51 publications

References 30 publications

Solvent LiCl–KCl in the nephelauxetic series for trivalent rare earths

Solvent LiCl–KCl in the nephelauxetic series for trivalent rare earths

Electronic absorption spectra of lanthanides in a molten chloride

Spectrophotometric Study of Nd²⁺ Ions in LiCl-KCl Eutectic Melt

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Absorption Spectra of the Lanthanides in Fused Lithium Chloride-Potassium Chloride Eutectic

Cited by 51 publications

References 30 publications

Solvent LiCl–KCl in the nephelauxetic series for trivalent rare earths

Solvent LiCl–KCl in the nephelauxetic series for trivalent rare earths

Electronic absorption spectra of lanthanides in a molten chloride

Spectrophotometric Study of Nd2+ Ions in LiCl-KCl Eutectic Melt

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Spectrophotometric Study of Nd²⁺ Ions in LiCl-KCl Eutectic Melt