CsBr-TmBr3-H2O和CsBr-TmBr3-HBr(~13%)-H2O(298.15 K)的相平衡及新固相化合物的热力学和荧光性质

doi:10.7503/cjcu20150187

摘要/Abstract

摘要：

采用等温溶度法测量了三元体系CsBr-TmBr₃-H₂O和四元体系CsBr-TmBr₃-HBr(~13%)-H₂O在298.15 K时的相平衡溶度数据, 并绘制了相应的相图. 三元体系和四元体系均由3个平衡固相CsBr, Cs₃Tm₂Br₉·16H₂O和TmBr₃·8H₂O构成. 新固相化合物Cs₃Tm₂Br₉·16H₂O在三元和四元体系均是固液异成分溶解的化合物, 且其结晶区随平衡液相中氢溴酸浓度的增加而增大. 用X射线粉末衍射仪(XRD)、热重分析仪和荧光光谱仪对Cs₃Tm₂Br₉·16H₂O进行了表征. 结果表明, 当用712 nm光激发时, Cs₃Tm₂Br₉·16H₂O在471 nm处具有上转换发光性能. 用微量热仪测定了Cs₃Tm₂Br₉·16H₂O在无限稀释下的标准摩尔溶解焓为-(11.63±0.46) kJ/mol, 确定其标准摩尔生成焓为-(7826.2±1.2) kJ/mol.

关键词: 相平衡, 溴化铯, 溴化铥, 标准摩尔生成焓, 荧光性质

Abstract:

The phase equilibria of the ternary system CsBr-TmBr₃-H₂O and the quaternary system CsBr-TmBr₃-HBr(~13%)-H₂O at 298.15 K were investigated by the isothermal solubility method. Based on the experimental data, the corresponding phase diagrams were plotted. In the ternary system, three crystallization regions corresponding to CsBr, Cs₃Tm₂Br₉·16H₂O and TmBr₃·8H₂O were found. Similarly, there were three crystallization regions corresponding to CsBr, Cs₃Tm₂Br₉·16H₂O and TmBr₃·8H₂O in the quaternary system. The phase diagrams of the ternary and quaternary systems were compared and a new double salt Cs₃Tm₂Br₉·16H₂O is formed which is incongruently soluble in the two systems; the area of the crystallization region of Cs₃Tm₂Br₉·16H₂O increases with the increasing concentration of HBr in the equilibrium liquid phase. The new solid-phase compound Cs₃Tm₂Br₉·16H₂O was characterized by chemical analysis, X-ray diffraction(XRD) and thermal gravity-differential thermal gravity(TG-DTG) techniques. The fluorescence excitation and emission spectra of Cs₃Tm₂Br₉·16H₂O were measured. Upconversion emission of the new solid phase was found at 471 nm when excited at 712 nm. The standard molar enthalpy of solution of Cs₃Tm₂Br₉·16H₂O in water was measured to be -(11.63±0.46) kJ/mol by microcalorimetry under the condition of infinite dilution and its standard molar enthalpy of formation was determined as -(7826.2±1.2) kJ/mol.

Key words: Phase diagram, Cesium bromide, Thulium bromide, Standard molar enthalpy of formation, Fluorescent property

中图分类号:

O642.4

TrendMD:

李赵婉, 乔占平, 陈欣, 党元林, 杨奇超. CsBr-TmBr₃-H₂O和CsBr-TmBr₃-HBr(~13%)-H₂O(298.15 K)的相平衡及新固相化合物的热力学和荧光性质. 高等学校化学学报, 2015, 36(9): 1759.

LI Zhaowan, QIAO Zhanping, CHEN Xin, DANG Yuanlin, YANG Qichao. Equilibria for the CsBr-TmBr₃-H₂O and CsBr-TmBr₃-HBr(~13%)-H₂O Systems at 298.15 K and Thermodynamic and Fluorescent Properties of New Solid-phase Compound. Chem. J. Chinese Universities, 2015, 36(9): 1759.

图/表 9

Table 1 Solubility data(mass fraction, %) for the ternary system CsBr-TmBr3-H2O at (298.15±0.1) K and (0.1±0.005) MPaa

No.	Saturated solution, w^b(%)		Wet residue, w(%)		Solid phase^c	No.	Saturated solution, w^b(%)		Wet residue, w(%)		Solid phase^c
No.	CsBr	TmBr₃			CsBr	TmBr₃		CsBr	TmBr₃	CsBr	TmBr₃
1	55.51	0			A	13	13.27	56.88	40.46	41.39	A+B
2	48.40	6.44	94.59	0.63	A	14	12.58	57.00	24.11	51.77	B
3	40.46	13.37	92.41	1.77	A	15	11.54	58.00	23.04	52.78	B
4	33.45	20.09	91.82	2.49	A	16	9.90	59.66	20.91	54.28	B
5	29.88	24.58	90.61	3.33	A	17	8.83	60.99	14.98	59.40	B+C
6	25.87	29.73	89.52	4.18	A	18	8.70	60.75	10.29	63.33	B+C
7	22.21	34.74	88.29	5.48	A	19	8.88	60.47	5.59	67.24	B+C
8	18.99	39.05	90.07	4.64	A	20	6.29	62.36	2.27	69.74	C
9	16.09	45.53	82.54	9.94	A	21	4.29	63.31	1.77	67.79	C
10	14.86	49.22	81.76	10.57	A	22	2.75	64.29	1.42	67.83	C
11	14.40	51.57	82.03	10.94	A	23	0	65.67			C
12	13.82	54.72	82.47	11.47	A

Fig.1 Phase diagram for the ternary system CsBr-TmBr3-H2O at 298.15 KE1 and E2 stand for double saturation point. B and C stand for Cs3Tm2Br9·16H2O and TmBr3·8H2O, respectively.

Fig.2 Phase diagram for the quaternary system CsBr-TmBr3-HBr(~13%)-H2O projected on CsBr-TmBr3-H2O at 298.15 KE1 and E2 stand for double saturation point. B and C stand for Cs3Tm2Br9·16H2O and TmBr3·8H2O, respectively.

Table 2 Solubility data(mass fraction, %) of the saturated solution of the quaternary system CsBr-TmBr3-HBr(13.09%)-H2O and central projection data on the trigonal basal face CsBr-TmBr3-H2O at (298.15±0.1) K and (0.1±0.005) MPaa

No.	Composition of solution, w(%)					Composition of residue, w(%)					Solid phase^c
	In the tetrahedron			In the trigonal basal face^b			In the tetrahedron			In the trigonal basal face
	HBr	CsBr		TmBr₃	CsBr	TmBr₃	HBr	CsBr	TmBr₃	CsBr	TmBr₃
1	12.46	36.77	0.00	42.00	0.00						A
2	13.81	30.76	5.02	35.69	5.83	1.83	91.28	0.69	92.98	0.71	A
3	13.06	24.84	11.93	28.58	13.73	1.84	91.93	1.35	93.66	1.37	A
4	13.88	18.90	22.08	21.94	25.64	1.96	89.45	3.02	91.24	3.08	A
5	13.45	15.88	29.02	18.34	33.53	1.60	90.15	3.23	91.61	3.28	A
6	13.57	15.17	34.69	17.55	40.13	2.33	86.34	5.59	88.40	5.72	A
7	13.89	14.64	36.42	17.00	42.30	2.55	85.03	6.61	87.25	6.78	A
8	13.76	14.77	37.42	17.13	43.39	2.56	83.54	6.53	85.73	6.70	A
9	13.24	15.40	39.09	17.75	45.05	6.51	36.32	42.22	38.85	45.16	A+B
10	13.05	13.11	40.82	15.08	46.95	6.63	28.25	43.11	30.26	46.18	B
11	13.45	11.07	42.86	12.79	49.52	6.11	28.27	43.92	30.11	46.77	B
12	12.40	8.82	46.33	10.07	52.89	5.66	26.84	45.62	28.45	48.36	B
13	12.72	8.25	46.23	9.45	52.97	4.26	16.33	55.57	17.06	58.04	B+C
14	12.70	8.66	46.25	9.93	52.98	3.77	2.53	65.86	2.63	68.44	C
15	12.52	4.59	48.61	5.25	55.57	3.08	1.53	67.96	1.58	70.12	C
16	12.33	1.87	50.22	2.13	57.28	2.80	1.00	68.79	1.03	70.77	C
17	12.28	0.00	51.46	0.00	58.66						C

Fig.3 XRD pattern of Cs3Tm2Br9·16H2O

Fig.4 TG-DTG curves of Cs3Tm2Br9·16H2O

Table 3 Molar enthalpy of solution of Cs3Tm2Br9·16H2O in deionized water at (298.15±0.01) Ka

No.	m/mg	Q_s/mJ	Δ_sol $H m 0 —$ /(kJ·mol^-1)
1	64.80	-416.9	-11.22
2	65.72	-449.7	-11.93
3	65.27	-445.5	-11.90
4	67.88	-470.1	-12.07
5	63.79	-404.3	-11.05
Mean^b	-(11.63±0.46)

Table 3 Molar enthalpy of solution of Cs3Tm2Br9·16H2O in deionized water at (298.15±0.01) Ka

No.	m/mg	Q_s/mJ	Δ_sol $H m 0 —$ /(kJ·mol^-1)
1	64.80	-416.9	-11.22
2	65.72	-449.7	-11.93
3	65.27	-445.5	-11.90
4	67.88	-470.1	-12.07
5	63.79	-404.3	-11.05
Mean^b	-(11.63±0.46)

Fig.5 Excitation spectrum of Cs3Tm2Br9·16H2O(λem=471 nm)

Fig.6 Upconversion luminescence spectrum of Cs3Tm2Br9·16H2O(λex=712 nm)

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CsBr-TmBr₃-H₂O和CsBr-TmBr₃-HBr(~13%)-H₂O(298.15 K)的相平衡及新固相化合物的热力学和荧光性质

Equilibria for the CsBr-TmBr₃-H₂O and CsBr-TmBr₃-HBr(~13%)-H₂O Systems at 298.15 K and Thermodynamic and Fluorescent Properties of New Solid-phase Compound

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