The Fluorescence of Uranium Trioxide Hydrates1

Dwayne T. Vier; Melvin L. Schultz; Jacob Bigeleisen

doi:10.1364/JOSA.38.000811

Journal of the Optical Society of America
Vol. 38,
Issue 9,
pp. 811-814
(1948)
•https://doi.org/10.1364/JOSA.38.000811

The Fluorescence of Uranium Trioxide Hydrates

Dwayne T. Vier, Melvin L. Schultz, and Jacob Bigeleisen

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Dwayne T. Vier, Melvin L. Schultz, and Jacob Bigeleisen, "The Fluorescence of Uranium Trioxide Hydrates1," J. Opt. Soc. Am. 38, 811-814 (1948)

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Abstract

The hydrates of uranium trioxide have been found to be fluorescent when exposed to ultraviolet light. The fluorescence spectra of the different hydrates have been measured. The anhydrous oxides do not fluoresce.

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Hydrate	Crystal form	X-ray classification	Starting material	Sample no.	Treatment in water
Hydrate	Crystal form	X-ray classification	Starting material	Sample no.	time hr.	temp. °C
UO₃·2H₂O	micro crystalline	I	P	219.123.2	44	77
UO₃·2H₂O	micro crystalline	IIA	M	235.39.2	192	28
UO₃·H₂O	rhombic hexagonal tablets, 5μ	IIA	P	219.108.1	89	100
UO₃·H₂O	amorphous and some 5μ rhombic hexagons	IIB	M	219.92.3	600	100
UO₃·H₂O	rhombic rods, 5×30μ	IIC	P	219.46.2	264	185
UO₃·H₂O	triclinic, 30μ	III	M	235.38	340	185
${UO}_{3} \cdot \frac{1}{2} H_{2} O$	monoclinic, 50μ	IV	P	235.26	96	325–350

Hydrate	X-ray classification	Description of fluorescence spectrum
Hydrate	X-ray classification	298°K	77°K
UO₃·2H₂O	I	bands	bands
UO₃·2H₂O	IIA	continuous	bands
UO₃·H₂O	IIA	no fluorescence	bands
UO₃·H₂O	IIB	no fluorescence	bands
UO₃·H₂O	IIC	no fluorescence	bands
UO₃·H₂O	III	nearly continuous, spectrum displaced toward blue	bands
${UO}_{3} \cdot \frac{1}{2} H_{2} O$	IV	weak fluorescence	bands

A: UO₃·2H₂O, X-ray type I: Sample 219.123.2.
	20°K			77°K
Band	Description of line	$\tilde{ν}$ , cm⁻¹	$\tilde{ν}$ , cm⁻¹	Description of line
I	Fluorescence begins	19900
	Strong, broad	19740	19766	Moderate, broad
	Moderate, diffuse	19530	19542	Weak, diffuse
	Moderate, very diffuse	19150	19245	Weak, very diffuse
II	Strong, diffuse	18920	18937	Strong, broad
	Weak, very diffuse	18740	18706	Weak, diffuse
	Weak, very diffuse	18410	18472	Weak, very diffuse
III	Moderate, diffuse	18080	18090	Moderate, broad
IV	Weak, very diffuse	17420	present	Weak, very diffuse

First band at 19,740 cm⁻¹. Bands repeat every 833±9 cm⁻¹. Secondary lines in bands at 200 cm⁻¹ and 550 cm⁻¹ from initial line. (Note: the average deviation given after frequency with which bands repeat is probably much less than the actual error in this and all other tables.)			The bands are fairly sharp with structure. Total intensity is low. First band at 19,766 cm⁻¹; bands repeat every 838±9 cm⁻¹. Secondary lines in bands at 230 cm⁻¹ and 500 cm⁻¹ from initial line.

B: UO₃·2H₂O, X-ray type IIA; Sample 235.39.2.

I	Fluorescence begins	19900
	Moderate, very diffuse; shaded to red	19720	19540	Weak, very diffuse
II	Strong, very diffuse	18920	18820	Moderate, very diffuse; shaded to red
III	Moderate, very diffuse	18110	17961	Weak, very diffuse; shaded to red
IV	Extremely weak, very diffuse	present	present	Very weak, very diffuse

Bands similar to x-ray type I except for absence of secondary structure. First band at 19720 cm⁻¹ Bands repeat every 805±5 cm⁻¹.			Bands very diffuse. Total intensity high. First band at 19540 cm⁻¹. Bands repeat every 790±70 cm⁻¹.

C: UO₃·H₂O, X-ray type IIA; Sample 219.108.1.

I	Fluorescence begins	19990
	Moderate, very diffuse; shaded to red	19730	19549	Weak, very diffuse
II	Strong, very diffuse	18860	18640	Moderate, very diffuse; shaded to red
III	Moderate, very diffuse	18050	17888	Weak, very diffuse; shaded to red
IV			present

Spectrum almost identical with that of UO₃·2H₂O, x-ray type IIA. First band at 19730 cm⁻¹. Bands repeat every 835±25 cm⁻¹.			Spectrum almost identical with that of UO₃·2H₂O, x-ray type IIA. Bands very diffuse. Total intensity moderate. First band at 19549 cm⁻¹. Bands repeat every 831±79 cm⁻¹.

D: UO₃·H₂O, X-ray type IIB; Sample 219.92.3.

I	Fluorescence begins	19875
	Moderate, sharp	19846.7	19866	Moderate
	Weak, narrow	19821.3
	Weak, narrow (also center of broad band)	19773	19791	Weak
	Weak, narrow	19570.2	19584.	Weak, broad
	Weak, narrow	19549.3
	Moderate, broad	19446	19470	Weak, broad
	Moderate, broad	19420
	Moderate, broad	19274	19300	Weak, diffuse
	Moderate, broad	19181	present	Very weak
	Weak, narrow	19030.5
II	Strong, narrow	18998.9	18997	Strong, broad
	Very weak, narrow	18974
	Strong, diffuse	18909	18919	Strong
	Strong, diffuse	18732	18745	Weak, diffuse
	Strong, diffuse	18631	18605	Weak, diffuse
III	Strong, diffuse	18140	18190	Moderate, broad
	Strong, diffuse	18050	18067	Moderate, broad
	Very weak, very diffuse	17870	17918	Weak, diffuse
	Weak, diffuse	17800	17817	Weak, diffuse
IV	Weak, very diffuse	17330	17349	Weak, very diffuse
	Moderate, very diffuse	17180
V			present	Extremely weak, very diffuse

First band at 19846.7 cm⁻¹. Bands repeat every 839±19 cm”¹. Secondary lines in bands at 25 cm⁻¹, 90 cm⁻¹, 270 cm⁻¹, and 380 cm⁻¹ from initial line.			Bands fairly sharp, with structure. Total intensity moderate. First band at 19866 cm⁻¹. Bands repeat every 839±21 cm⁻¹. Secondary lines in bands at 80 cm⁻¹, 270 cm⁻¹, and 380 cm⁻¹ from initial line.

E: UO₃·H₂O, X-ray type IIC; Sample 219.46.2.

I	Fluorescence begins	19797
	Moderate, sharp	19744.5	19832	Very weak
	Strong, sharp	19711.6
	Moderate, narrow	19676.8
	Moderate, narrow	19640.0	19635	Moderate, very diffuse
	Moderate, narrow	19503.8
	Moderate, sharp	19467.0
	Moderate	19152	present	Very weak
II	Moderate	19009.7	19004	Weak, broad
	Strong, narrow	18991.6
	Strong	18946.6
	Strong, very diffuse	18896.2	18840	Strong, very diffuse
III	Strong, very diffuse	18080	18157	Weak, diffuse
	Strong, very diffuse	17980	17976	Moderate, very diffuse
IV	Moderate, very diffuse	(17240)	17085	Weak, very diffuse
V			present	Very weak, very diffuse

First band at 19744.5 cm⁻¹. Band structure does not appear to repeat. Bands repeat at 835±20 cm⁻¹.			Bands diffuse. Total intensity high. First band at 19832 cm⁻¹. Bands repeat at 849±15 cm⁻¹.

F: UO₃·H₂O, X-ray type III; Sample 235.38.

I	Fluorescence begins	20030
	Very weak, narrow	19988.6
	Weak, narrow	19962.9
	Weak, narrow	19938.2
	Moderate, narrow	19876.8
	Moderate	19825.9
	Moderate, narrow	19773.0
	Weak	19740.2
	Weak	19711.0
	Strong, very diffuse	19640	19681	Weak, very diffuse
	Moderate, very diffuse	19120	19009	Very weak, very diffuse
II	Strong, very diffuse	18860	18833	Strong, very diffuse
III	Strong, very diffuse	18110	17993	Weak, very diffuse
IV	Moderate, very diffuse	17360	present	Very weak, very diffuse

First band at 19988.6 cm⁻¹. Bands repeat (but not the structure) every 760±13 cm⁻¹.			Bands diffuse. Total intensity low. First band at 19681 cm⁻¹. Bands repeat every 844±4 cm⁻¹

G: ${UO}_{3} \cdot \frac{1}{2} H_{2} O$ , X-ray type IV; Sample 235.26.

I	Strong, very sharp	19711.9
	Weak, narrow	19009.4
	Weak, narrow	18992.1
	Moderate, sharp	18946.8		Absent
	Moderate, sharp	18913.4
	Strong	18845
II	Strong, broad	18764.2	(18780)	Fluorescence begins, very diffuse
	Moderate, sharp	18755.4
	Moderate, narrow	18672.5
	Moderate, narrow	18656.1
	Strong, narrow	18463.1	(18600)	Weak, narrow
III	Moderate, broad	18048.7	(18190)	Weak, narrow
	Moderate, broad	18023.8
	Strong, narrow	17967.3	(18070)	Weak, narrow
	Strong, narrow	17910.3
	Weak, broad	17883.8
	Moderate, broad	17760	(17920)	Very weak, broad
	Moderate, broad	17630	(17820)	Very weak, broad
IV	Moderate, very diffuse	(17180)	(17180)	Very weak, very diffuse

Total intensity high. First band at 19711.9 cm⁻¹. Band structure does not appear to repeat, nor are the intervals between band peaks equal.			Fluorescence, but too weak to measure accurately. Very diffuse bands also present. First band begins at 18780 cm⁻¹. Spectrum very much like x-ray type IIB, but first two strong bands are missing.

Hydrate	Crystal form	X-ray classification	Starting material	Sample no.	Treatment in water
Hydrate	Crystal form	X-ray classification	Starting material	Sample no.	time hr.	temp. °C
UO₃·2H₂O	micro crystalline	I	P	219.123.2	44	77
UO₃·2H₂O	micro crystalline	IIA	M	235.39.2	192	28
UO₃·H₂O	rhombic hexagonal tablets, 5μ	IIA	P	219.108.1	89	100
UO₃·H₂O	amorphous and some 5μ rhombic hexagons	IIB	M	219.92.3	600	100
UO₃·H₂O	rhombic rods, 5×30μ	IIC	P	219.46.2	264	185
UO₃·H₂O	triclinic, 30μ	III	M	235.38	340	185
${UO}_{3} \cdot \frac{1}{2} H_{2} O$	monoclinic, 50μ	IV	P	235.26	96	325–350

Hydrate	X-ray classification	Description of fluorescence spectrum
Hydrate	X-ray classification	298°K	77°K
UO₃·2H₂O	I	bands	bands
UO₃·2H₂O	IIA	continuous	bands
UO₃·H₂O	IIA	no fluorescence	bands
UO₃·H₂O	IIB	no fluorescence	bands
UO₃·H₂O	IIC	no fluorescence	bands
UO₃·H₂O	III	nearly continuous, spectrum displaced toward blue	bands
${UO}_{3} \cdot \frac{1}{2} H_{2} O$	IV	weak fluorescence	bands

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Journal of the Optical Society of America