Absorption Spectra of Molten Fluoride Salts.  Solutions of Several Metal Ions in Molten Lithium Fluoride-Sodium Fluoride-Potassium Fluoride

Young, J. P.; White, J.C.

doi:10.1021/ac60163a020

Cited by 39 publications

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References 21 publications

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“…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).…”

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confidence: 99%

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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confidence: 99%

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

Johnson¹,

Sandoe²

1968

Can. J. Chem.

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“…, 19, 2242 (---) LiF-NaF-KF eutectic at 650 °C. 15 The fluoride spectrum is considerably enhanced, but the absorbancies cannot be expressed on an absolute scale due to the experimental method used for recording the spectrum.15 to a suitable amount, and Cr(III) was added again in successive steps and so forth. This procedure was adopted in order to obtain a maximum number of measured data during one experimental run.…”

Section: Methodsmentioning

confidence: 99%

Stepwise formation of fluoride complexes of chromium(III) in mixed potassium thiocyanate-potassium fluoride molten salts

Holmberg¹,

Jarring²

1987

Inorg. Chem.

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“…For that reason, a few experimental works have been performed by using spectroscopic techniques in the molten halide salts. The absorption spectroscopic properties of most lanthanides in various molten halide salts have been analyzed to investigate the structural symmetry of chemical constitution and redox behaviors and to determine their molar absorptivities for the purpose of quantification [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. However, the absorption spectra and the molar absorptivities in those literature works have not been completely reported for all lanthanide series.…”

Section: Introductionmentioning

confidence: 99%