锂钠镁共存硫酸盐体系多温相图及其应用研究

doi:10.11949/0438-1157.20240169

摘要/Abstract

摘要：

针对硫酸钠亚型盐湖卤水钠锂比高、镁锂比高带来的锂分离难题，通过开展锂钠镁共存硫酸盐体系多温相图研究，获取锂钠镁硫酸盐之间的作用关系和结晶析出规律，并应用于指导降低卤水中钠镁含量工艺设计。采用等温溶解平衡法获取了四元体系Li⁺， Na⁺， Mg²⁺//SO₄^2- - H₂O 303.2、318.2 K固液相平衡数据，采用X-ray粉晶衍射法（XRD）测定了共饱点的平衡固相类型。复盐分析：采用X-ray粉晶衍射法（XRD）、扫描电镜（SEM）和热重分析法（TG-DSC）进行了各复盐的晶体结构分析、晶体形貌表征和热分析。研究发现：四元体系Li⁺， Na⁺， Mg²⁺//SO₄^2- - H₂O 303.2、318.2 K下均为复杂体系，相图均包含4个四元共饱点、9条单变量曲线和6个结晶区。303.2 K时，该体系相图结晶区为：Na₂SO₄、Na₂SO₄·10H₂O、Li₂SO₄·H₂O、MgSO₄·7H₂O、Na₂SO₄·MgSO₄·4H₂O、Li₂SO₄·3Na₂SO₄·12H₂O；318.2 K时，该体系相图结晶区为：Na₂SO₄、MgSO₄·7H₂O、Li₂SO₄·H₂O、Na₂SO₄·MgSO₄·4H₂O、Li₂SO₄·Na₂SO₄、Li₂SO₄·3Na₂SO₄·12H₂O。对比该四元体系288.2、298.2、303.2、318.2、323.2 K多温相图发现：温度对体系的影响主要表现在水合盐和含锂复盐的结晶形式及各盐类结晶区面积的变化。根据四元体系多温相图中含锂复盐（Li₂SO₄·Na₂SO₄、Li₂SO₄·3Na₂SO₄·12H₂O）、白钠镁矾（Na₂SO₄·MgSO₄·4H₂O）和三元体系Na⁺， Mg²⁺//SO₄^2- - H₂O多温相图中盐类的结晶规律，给出了硫酸钠亚型盐湖脱钠镁及白钠镁矾的分离加工建议。

关键词: 相平衡, 溶液, 溶解性, 白钠镁矾, 含锂复盐

Abstract:

In order to solve the problem of lithium separation caused by high ratio of sodium to lithium and high ratio of magnesium to lithium in sodium sulfate subtype salt lake brine, the multi-temperature phase diagram of lithium-sodium-magnesium coexistence sulfate system was studied to obtain the action relationship and crystallization precipitation law of lithium-sodium-magnesium sulfate. It is applied to guide the process design of reducing the content of sodium and magnesium in brine. The solid-liquid phase equilibria for the quaternary systems Li⁺, Na⁺, Mg²⁺//SO₄^2- - H₂O at 303.2 and 318.2 K were studied by using isothermal dissolution equilibrium method. The solid phases of invariant points were verified by X-ray diffraction method (XRD). The crystal structure, crystal morphology and thermal analysis of the double salts were analyzed by X-ray diffraction method (XRD), scanning electron microscope (SEM) and thermogravimetric analysis (TG-DSC). Results show that both these systems are complex systems, and their phase diagrams consist of these quaternary systems consist of four invariant points, nine isothermal dissolution curves, and six crystallization regions. The crystallization regions of the phase diagram of the system at 303.2 K is Na₂SO₄, Na₂SO₄·10H₂O, Li₂SO₄·H₂O, MgSO₄·7H₂O, Na₂SO₄·MgSO₄·4H₂O, Li₂SO₄·3Na₂SO₄·12H₂O; 318.2 K is Na₂SO₄, Li₂SO₄·H₂O, MgSO₄·7H₂O, Na₂SO₄·MgSO₄·4H₂O, Li₂SO₄·3Na₂SO₄·12H₂O, Li₂SO₄·Na₂SO₄. By comparing the multi-temperature phase diagrams of the quaternary system at 288.2, 298.2, 303.2, 318.2 and 323.2 K, it is found that the effect of temperature on the system is mainly manifested in the crystallization form of hydrated salts and lithium-containing double salts and the change of crystallization areas of each salts. Combined with the crystallization rules of lithium-containing double salts (Li₂SO₄·Na₂SO₄, Li₂SO₄·3Na₂SO₄·12H₂O), astrakhanite (Na₂SO₄·MgSO₄·4H₂O) in Quaternary system and the crystallization rules of salts in ternary system Na⁺, Mg²⁺//SO₄^2- - H₂O, some suggestions for the separation and processing of sodium sulfate subtype salt lake removal sodium (magnesium) and astrakhanite separation process were given.

Key words: phase equilibria, solution, solubility, astrakhanite, lithium-containing double salt

中图分类号:

O 642.4

赵志星, 姚智豪, 于雪峰, 杨游胜, 曾英, 于旭东. 锂钠镁共存硫酸盐体系多温相图及其应用研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240169.

Zhixing ZHAO, Zhihao YAO, Xuefeng YU, Yousheng YANG, Ying ZENG, Xudong YU. Multi-temperature phase diagram of lithium-sodium-magnesium coexistence sulfate system and its application[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240169.

图/表 9

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编号	密度/ (g·cm^-3)	折光率 n_D	平衡液相组成, w(B)×10²				干盐指数(g/100g盐)				平衡固相
			平衡液相组成, w(B)×10²				J(Li₂SO₄) + J(Na₂SO₄) + J(MgSO₄) = 100
			w(Li₂SO₄)	w(Na₂SO₄)	w(MgSO₄)	w(H₂O)	J(Li₂SO₄)	J(Na₂SO₄)	J(MgSO₄)	J(H₂O)
T = 303.2 K
1, A	1.3134	1.3785	4.95	27.39	0.00	67.67	15.30	84.70	0.00	209.29	Mir + Db1
2	1.3247	1.3812	4.68	25.93	1.98	67.41	14.36	79.58	6.06	206.85	Mir + Db1
3	1.3317	1.3834	4.42	24.29	3.96	67.33	13.53	74.34	12.12	206.06	Mir + Db1
4	1.3361	1.3850	4.23	23.53	5.75	66.48	12.63	70.20	17.17	198.37	Mir + Db1
5	1.3431	1.3870	4.00	22.31	7.43	66.26	11.85	66.12	22.03	196.35	Mir + Db1
6	1.3519	1.3884	3.85	21.52	8.74	65.90	11.28	63.10	25.63	193.26	Th + Db1
7	1.3543	1.3900	3.67	20.75	10.43	65.15	10.53	59.54	29.93	186.92	Th + Db1
8	1.3669	1.3916	3.53	20.35	11.60	64.53	9.94	57.37	32.70	181.91	Th + Db1
9	1.3692	1.3925	3.61	20.05	12.72	63.62	9.94	55.09	34.97	174.85	Th + Db1
10, B	1.3630	1.3859	0.00	27.40	8.18	64.42	0.00	77.01	22.99	181.06	Th + Mir
11	1.3524	1.3857	1.58	26.46	7.91	64.06	4.39	73.61	22.00	178.23	Th + Mir
12	1.3480	1.3855	2.39	25.94	7.84	63.82	6.62	71.70	21.68	176.37	Th + Mir
13	1.3475	1.3860	3.61	24.53	8.40	63.46	9.89	67.13	22.98	173.67	Th + Mir
14, S₁	1.3473	1.3856	4.26	23.14	8.28	64.32	11.94	64.85	23.21	180.26	Th + Mir + Db1
15	1.3721	1.3943	3.14	18.52	13.48	64.86	8.95	52.69	38.37	184.55	Ast + Db1
16	1.3801	1.3954	3.18	15.98	16.33	64.51	8.97	45.02	46.01	181.78	Ast + Db1
17	1.3814	1.3959	3.31	15.91	18.04	62.74	8.88	42.70	48.41	168.40	Ast + Db1
18	1.3959	1.3991	3.17	14.55	20.05	62.23	8.39	38.52	53.08	164.78	Ast + Db1
19	1.3993	1.3997	3.07	13.34	21.44	62.16	8.11	35.24	56.65	164.24	Ast + Db1
20	1.3944	1.3997	3.10	13.04	22.12	61.74	8.09	34.08	57.83	161.39	Ast + Db1
21, C	1.3756	1.3930	0.00	22.96	13.34	63.70	0.00	63.25	36.75	175.51	Ast + Th
22	1.3802	1.3930	0.61	22.43	13.22	63.74	1.69	61.86	36.46	175.82	Ast + Th
23	1.3874	1.3937	1.28	22.21	13.00	63.51	3.50	60.87	35.64	174.02	Ast + Th
24	1.3917	1.3942	2.60	21.06	12.79	63.56	7.13	57.78	35.09	174.39	Ast + Th
25, S₂	1.3806	1.3935	3.33	19.55	12.88	64.24	9.31	54.68	36.01	179.65	Ast + Th + Db1
26, D	1.3850	1.3976	0.00	12.30	23.10	64.60	0.00	34.74	65.26	182.51	Ast + Eps
27	1.3802	1.3974	1.48	11.65	22.44	64.43	4.15	32.76	63.09	181.11	Ast + Eps
28	1.3816	1.3975	2.43	11.94	22.65	62.97	6.57	32.26	61.17	170.07	Ast + Eps
29, S₃	1.3880	1.3977	2.98	11.28	21.51	64.23	8.33	31.53	60.14	179.53	Ast + Eps + Db1
30	1.3809	1.3980	3.69	11.18	21.18	63.95	10.23	31.02	58.75	177.42	Eps + Db1
31	1.3816	1.3982	4.61	10.49	20.85	64.04	12.82	29.19	58.00	178.11	Eps + Db1
32	1.3828	1.3986	6.06	9.36	20.46	64.12	16.89	26.09	57.02	178.69	Eps + Db1
33	1.3881	1.3998	8.75	8.95	19.54	62.76	23.49	24.04	52.47	168.54	Eps + Db1
34	1.3960	1.4003	10.40	9.08	17.85	62.67	27.86	24.32	47.82	167.85	Eps + Db1
35	1.3951	1.4005	11.50	8.90	17.32	62.27	30.50	23.59	45.91	165.07	Eps + Db1
36, S₄	1.3986	1.4007	12.21	8.15	17.36	62.28	32.36	21.60	46.04	165.14	Eps + Db1 + Ls
37, E	1.3451	1.3970	13.60	0.00	20.91	65.49	39.40	0.00	60.60	189.80	Eps + Ls
38	1.3467	1.3972	13.53	2.16	19.44	64.86	38.52	6.16	55.33	184.59	Eps + Ls
39	1.3560	1.3976	13.36	3.19	19.02	64.42	37.56	8.98	53.46	181.08	Eps + Ls
40	1.3598	1.3983	13.18	4.29	18.88	63.64	36.27	11.79	51.94	175.06	Eps + Ls
41	1.3657	1.3988	12.94	5.26	18.67	63.12	35.10	14.26	50.64	171.17	Eps + Ls
42	1.3717	1.3996	12.59	6.67	18.54	62.20	33.32	17.65	49.03	164.53	Eps + Ls
43	1.3885	1.4003	12.28	7.73	17.88	62.11	32.40	20.41	47.18	163.93	Eps + Ls
44, F	1.3051	1.3842	20.63	12.64	0.00	66.72	62.01	37.99	0.00	200.50	Db1 + Ls
45	1.3119	1.3861	19.12	11.73	2.33	66.83	57.62	35.36	7.01	201.46	Db1 + Ls
46	1.3235	1.3880	17.92	11.11	4.49	66.48	53.46	33.13	13.41	198.32	Db1 + Ls
47	1.3375	1.3910	16.26	10.67	7.93	65.14	46.64	30.60	22.76	186.88	Db1 + Ls
48	1.3529	1.3939	14.52	9.85	11.08	64.56	40.96	27.79	31.25	182.14	Db1 + Ls
49	1.3583	1.3947	13.78	9.52	12.39	64.31	38.61	26.69	34.71	180.22	Db1 + Ls
50	1.3757	1.3974	12.17	9.02	15.76	63.05	32.94	24.40	42.65	170.61	Db1 + Ls
T = 318.2 K
51, G	1.3300	1.3830	13.36	21.83	0.00	64.81	37.97	62.03	0.00	184.14	Db1 + Db2
52	1.3636	1.3852	12.99	21.03	3.13	62.85	34.98	56.61	8.41	169.16	Db1 + Db2
53	1.3676	1.3878	11.78	20.37	6.06	61.79	30.84	53.31	15.85	161.75	Db1 + Db2
54	1.3730	1.3906	11.03	18.75	8.11	62.11	29.11	49.49	21.40	163.94	Db1 + Db2
55	1.3808	1.3918	10.47	17.75	10.20	61.58	27.25	46.21	26.55	160.28	Db1 + Db2
56, T₁	1.3928	1.3931	9.75	17.34	10.64	62.28	25.84	45.96	28.20	165.11	Db1 + Db2 + Ast
57	1.3641	1.3921	9.49	18.70	10.12	61.68	24.77	48.81	26.42	160.95	Db1 + Ast
58	1.3708	1.3922	9.61	17.63	10.16	62.60	25.70	47.15	27.15	167.36	Db1 + Ast
59, H	1.3331	1.3812	9.68	24.67	0.00	65.65	28.18	71.82	0.00	191.16	Db1 + Th
60	1.3443	1.3845	9.32	23.39	2.08	65.21	26.80	67.23	5.97	187.48	Db1 + Th
61	1.3636	1.3880	9.31	22.38	4.54	63.77	25.70	61.78	12.52	176.00	Db1 + Th
62	1.3755	1.3901	8.50	20.24	7.07	64.20	23.73	56.52	19.75	179.29	Db1 + Th
63	1.3847	1.3924	8.47	19.97	9.23	62.33	22.49	53.00	24.51	165.44	Db1 + Th
64, I	1.3492	1.3886	0.00	22.93	12.74	64.32	0.00	64.28	35.72	180.28	Ast + Th
65	1.3568	1.3888	2.60	21.97	12.05	63.38	7.09	60.01	32.90	173.07	Ast + Th
66	1.3579	1.3897	5.13	21.07	11.16	62.65	13.74	56.40	29.86	167.71	Ast + Th
67	1.3618	1.3908	7.50	20.35	10.94	61.21	19.34	52.46	28.20	157.83	Ast + Th
68, T₂	1.3625	1.3913	8.69	19.85	10.01	61.46	22.54	51.49	25.97	159.47	Ast + Th + Db1
69	1.3829	1.3935	9.84	17.23	11.93	61.00	25.24	44.18	30.58	156.43	Db2 + Ast
70	1.3842	1.3938	9.35	15.41	13.08	62.16	24.70	40.74	34.57	164.28	Db2 + Ast
71	1.3827	1.3954	9.00	12.59	16.20	62.21	23.82	33.32	42.86	164.60	Db2 + Ast
72	1.3829	1.3958	8.67	10.65	18.47	62.21	22.95	28.18	48.87	164.62	Db2 + Ast
73	1.3906	1.3979	8.17	8.86	20.98	61.99	21.50	23.31	55.19	163.12	Db2 + Ast
74	1.4000	1.3992	7.77	7.55	22.69	61.99	20.44	19.87	59.69	163.09	Db2 + Ast
75	1.4012	1.3996	7.28	7.07	24.86	60.78	18.57	18.04	63.39	154.99	Db2 + Ast
76	1.4053	1.4004	6.59	6.32	25.98	61.11	16.94	16.26	66.80	157.12	Db2 + Ast
77, T₃	1.4083	1.4020	6.30	5.72	27.09	60.89	16.10	14.62	69.28	155.69	Db2 + Ast + Eps
78, J	1.4044	1.4005	0.00	7.75	29.13	63.12	0.00	21.02	78.98	171.14	Ast + Eps
79	1.4030	1.3994	1.69	7.30	27.61	63.40	4.62	19.94	75.43	173.25	Ast + Eps
80	1.4076	1.4008	3.39	6.62	26.39	63.60	9.31	18.20	72.49	174.70	Ast + Eps
81	1.4141	1.4014	5.19	5.61	25.34	63.85	14.36	15.53	70.12	176.66	Ast + Eps
82	1.4196	1.4033	6.83	4.70	26.65	61.82	17.90	12.31	69.79	161.93	Db2 + Eps
83	1.4088	1.4028	8.04	4.44	26.03	61.50	20.88	11.52	67.59	159.71	Db2 + Eps
84, K	1.3924	1.4030	10.35	0.00	26.34	63.31	28.20	0.00	71.80	172.54	Ls + Eps
85	1.4008	1.4038	10.09	1.45	27.43	61.03	25.88	3.72	70.40	156.64	Ls + Eps
86	1.4138	1.4052	9.68	3.22	26.92	60.18	24.31	8.08	67.61	151.15	Ls + Eps
87, T₄	1.4315	1.4058	8.70	4.59	26.49	60.22	21.86	11.53	66.61	151.40	Ls + Eps + Db2
88, L	1.2933	1.3820	20.98	11.60	0.00	67.41	64.39	35.61	0.00	206.87	Ls + Db2
89	1.3062	1.3840	19.48	11.00	2.17	67.35	59.66	33.70	6.63	206.31	Ls + Db2
90	1.3173	1.3860	18.53	10.82	4.68	65.97	54.46	31.79	13.75	193.89	Ls + Db2
91	1.3314	1.3896	17.16	10.15	8.70	63.99	47.66	28.19	24.16	177.71	Ls + Db2
92	1.3500	1.3921	15.11	9.31	11.94	63.64	41.57	25.60	32.83	175.06	Ls + Db2
93	1.3675	1.3950	14.23	8.63	13.75	63.40	38.87	23.57	37.56	173.20	Ls + Db2
94	1.3868	1.3979	12.64	7.83	18.98	60.55	32.03	19.84	48.13	153.52	Ls + Db2
95	1.4061	1.4008	11.30	7.17	21.67	59.86	28.16	17.85	53.99	149.10	Ls + Db2
96	1.4111	1.4028	10.16	6.22	22.85	60.77	25.89	15.86	58.24	154.87	Ls + Db2
97	1.4233	1.4050	9.54	4.84	27.01	58.60	23.06	11.68	65.26	141.57	Ls + Db2

编号	密度/ (g·cm^-3)	折光率 n_D	平衡液相组成, w(B)×10²				干盐指数(g/100g盐)				平衡固相
			平衡液相组成, w(B)×10²				J(Li₂SO₄) + J(Na₂SO₄) + J(MgSO₄) = 100
			w(Li₂SO₄)	w(Na₂SO₄)	w(MgSO₄)	w(H₂O)	J(Li₂SO₄)	J(Na₂SO₄)	J(MgSO₄)	J(H₂O)
T = 303.2 K
1, A	1.3134	1.3785	4.95	27.39	0.00	67.67	15.30	84.70	0.00	209.29	Mir + Db1
2	1.3247	1.3812	4.68	25.93	1.98	67.41	14.36	79.58	6.06	206.85	Mir + Db1
3	1.3317	1.3834	4.42	24.29	3.96	67.33	13.53	74.34	12.12	206.06	Mir + Db1
4	1.3361	1.3850	4.23	23.53	5.75	66.48	12.63	70.20	17.17	198.37	Mir + Db1
5	1.3431	1.3870	4.00	22.31	7.43	66.26	11.85	66.12	22.03	196.35	Mir + Db1
6	1.3519	1.3884	3.85	21.52	8.74	65.90	11.28	63.10	25.63	193.26	Th + Db1
7	1.3543	1.3900	3.67	20.75	10.43	65.15	10.53	59.54	29.93	186.92	Th + Db1
8	1.3669	1.3916	3.53	20.35	11.60	64.53	9.94	57.37	32.70	181.91	Th + Db1
9	1.3692	1.3925	3.61	20.05	12.72	63.62	9.94	55.09	34.97	174.85	Th + Db1
10, B	1.3630	1.3859	0.00	27.40	8.18	64.42	0.00	77.01	22.99	181.06	Th + Mir
11	1.3524	1.3857	1.58	26.46	7.91	64.06	4.39	73.61	22.00	178.23	Th + Mir
12	1.3480	1.3855	2.39	25.94	7.84	63.82	6.62	71.70	21.68	176.37	Th + Mir
13	1.3475	1.3860	3.61	24.53	8.40	63.46	9.89	67.13	22.98	173.67	Th + Mir
14, S₁	1.3473	1.3856	4.26	23.14	8.28	64.32	11.94	64.85	23.21	180.26	Th + Mir + Db1
15	1.3721	1.3943	3.14	18.52	13.48	64.86	8.95	52.69	38.37	184.55	Ast + Db1
16	1.3801	1.3954	3.18	15.98	16.33	64.51	8.97	45.02	46.01	181.78	Ast + Db1
17	1.3814	1.3959	3.31	15.91	18.04	62.74	8.88	42.70	48.41	168.40	Ast + Db1
18	1.3959	1.3991	3.17	14.55	20.05	62.23	8.39	38.52	53.08	164.78	Ast + Db1
19	1.3993	1.3997	3.07	13.34	21.44	62.16	8.11	35.24	56.65	164.24	Ast + Db1
20	1.3944	1.3997	3.10	13.04	22.12	61.74	8.09	34.08	57.83	161.39	Ast + Db1
21, C	1.3756	1.3930	0.00	22.96	13.34	63.70	0.00	63.25	36.75	175.51	Ast + Th
22	1.3802	1.3930	0.61	22.43	13.22	63.74	1.69	61.86	36.46	175.82	Ast + Th
23	1.3874	1.3937	1.28	22.21	13.00	63.51	3.50	60.87	35.64	174.02	Ast + Th
24	1.3917	1.3942	2.60	21.06	12.79	63.56	7.13	57.78	35.09	174.39	Ast + Th
25, S₂	1.3806	1.3935	3.33	19.55	12.88	64.24	9.31	54.68	36.01	179.65	Ast + Th + Db1
26, D	1.3850	1.3976	0.00	12.30	23.10	64.60	0.00	34.74	65.26	182.51	Ast + Eps
27	1.3802	1.3974	1.48	11.65	22.44	64.43	4.15	32.76	63.09	181.11	Ast + Eps
28	1.3816	1.3975	2.43	11.94	22.65	62.97	6.57	32.26	61.17	170.07	Ast + Eps
29, S₃	1.3880	1.3977	2.98	11.28	21.51	64.23	8.33	31.53	60.14	179.53	Ast + Eps + Db1
30	1.3809	1.3980	3.69	11.18	21.18	63.95	10.23	31.02	58.75	177.42	Eps + Db1
31	1.3816	1.3982	4.61	10.49	20.85	64.04	12.82	29.19	58.00	178.11	Eps + Db1
32	1.3828	1.3986	6.06	9.36	20.46	64.12	16.89	26.09	57.02	178.69	Eps + Db1
33	1.3881	1.3998	8.75	8.95	19.54	62.76	23.49	24.04	52.47	168.54	Eps + Db1
34	1.3960	1.4003	10.40	9.08	17.85	62.67	27.86	24.32	47.82	167.85	Eps + Db1
35	1.3951	1.4005	11.50	8.90	17.32	62.27	30.50	23.59	45.91	165.07	Eps + Db1
36, S₄	1.3986	1.4007	12.21	8.15	17.36	62.28	32.36	21.60	46.04	165.14	Eps + Db1 + Ls
37, E	1.3451	1.3970	13.60	0.00	20.91	65.49	39.40	0.00	60.60	189.80	Eps + Ls
38	1.3467	1.3972	13.53	2.16	19.44	64.86	38.52	6.16	55.33	184.59	Eps + Ls
39	1.3560	1.3976	13.36	3.19	19.02	64.42	37.56	8.98	53.46	181.08	Eps + Ls
40	1.3598	1.3983	13.18	4.29	18.88	63.64	36.27	11.79	51.94	175.06	Eps + Ls
41	1.3657	1.3988	12.94	5.26	18.67	63.12	35.10	14.26	50.64	171.17	Eps + Ls
42	1.3717	1.3996	12.59	6.67	18.54	62.20	33.32	17.65	49.03	164.53	Eps + Ls
43	1.3885	1.4003	12.28	7.73	17.88	62.11	32.40	20.41	47.18	163.93	Eps + Ls
44, F	1.3051	1.3842	20.63	12.64	0.00	66.72	62.01	37.99	0.00	200.50	Db1 + Ls
45	1.3119	1.3861	19.12	11.73	2.33	66.83	57.62	35.36	7.01	201.46	Db1 + Ls
46	1.3235	1.3880	17.92	11.11	4.49	66.48	53.46	33.13	13.41	198.32	Db1 + Ls
47	1.3375	1.3910	16.26	10.67	7.93	65.14	46.64	30.60	22.76	186.88	Db1 + Ls
48	1.3529	1.3939	14.52	9.85	11.08	64.56	40.96	27.79	31.25	182.14	Db1 + Ls
49	1.3583	1.3947	13.78	9.52	12.39	64.31	38.61	26.69	34.71	180.22	Db1 + Ls
50	1.3757	1.3974	12.17	9.02	15.76	63.05	32.94	24.40	42.65	170.61	Db1 + Ls
T = 318.2 K
51, G	1.3300	1.3830	13.36	21.83	0.00	64.81	37.97	62.03	0.00	184.14	Db1 + Db2
52	1.3636	1.3852	12.99	21.03	3.13	62.85	34.98	56.61	8.41	169.16	Db1 + Db2
53	1.3676	1.3878	11.78	20.37	6.06	61.79	30.84	53.31	15.85	161.75	Db1 + Db2
54	1.3730	1.3906	11.03	18.75	8.11	62.11	29.11	49.49	21.40	163.94	Db1 + Db2
55	1.3808	1.3918	10.47	17.75	10.20	61.58	27.25	46.21	26.55	160.28	Db1 + Db2
56, T₁	1.3928	1.3931	9.75	17.34	10.64	62.28	25.84	45.96	28.20	165.11	Db1 + Db2 + Ast
57	1.3641	1.3921	9.49	18.70	10.12	61.68	24.77	48.81	26.42	160.95	Db1 + Ast
58	1.3708	1.3922	9.61	17.63	10.16	62.60	25.70	47.15	27.15	167.36	Db1 + Ast
59, H	1.3331	1.3812	9.68	24.67	0.00	65.65	28.18	71.82	0.00	191.16	Db1 + Th
60	1.3443	1.3845	9.32	23.39	2.08	65.21	26.80	67.23	5.97	187.48	Db1 + Th
61	1.3636	1.3880	9.31	22.38	4.54	63.77	25.70	61.78	12.52	176.00	Db1 + Th
62	1.3755	1.3901	8.50	20.24	7.07	64.20	23.73	56.52	19.75	179.29	Db1 + Th
63	1.3847	1.3924	8.47	19.97	9.23	62.33	22.49	53.00	24.51	165.44	Db1 + Th
64, I	1.3492	1.3886	0.00	22.93	12.74	64.32	0.00	64.28	35.72	180.28	Ast + Th
65	1.3568	1.3888	2.60	21.97	12.05	63.38	7.09	60.01	32.90	173.07	Ast + Th
66	1.3579	1.3897	5.13	21.07	11.16	62.65	13.74	56.40	29.86	167.71	Ast + Th
67	1.3618	1.3908	7.50	20.35	10.94	61.21	19.34	52.46	28.20	157.83	Ast + Th
68, T₂	1.3625	1.3913	8.69	19.85	10.01	61.46	22.54	51.49	25.97	159.47	Ast + Th + Db1
69	1.3829	1.3935	9.84	17.23	11.93	61.00	25.24	44.18	30.58	156.43	Db2 + Ast
70	1.3842	1.3938	9.35	15.41	13.08	62.16	24.70	40.74	34.57	164.28	Db2 + Ast
71	1.3827	1.3954	9.00	12.59	16.20	62.21	23.82	33.32	42.86	164.60	Db2 + Ast
72	1.3829	1.3958	8.67	10.65	18.47	62.21	22.95	28.18	48.87	164.62	Db2 + Ast
73	1.3906	1.3979	8.17	8.86	20.98	61.99	21.50	23.31	55.19	163.12	Db2 + Ast
74	1.4000	1.3992	7.77	7.55	22.69	61.99	20.44	19.87	59.69	163.09	Db2 + Ast
75	1.4012	1.3996	7.28	7.07	24.86	60.78	18.57	18.04	63.39	154.99	Db2 + Ast
76	1.4053	1.4004	6.59	6.32	25.98	61.11	16.94	16.26	66.80	157.12	Db2 + Ast
77, T₃	1.4083	1.4020	6.30	5.72	27.09	60.89	16.10	14.62	69.28	155.69	Db2 + Ast + Eps
78, J	1.4044	1.4005	0.00	7.75	29.13	63.12	0.00	21.02	78.98	171.14	Ast + Eps
79	1.4030	1.3994	1.69	7.30	27.61	63.40	4.62	19.94	75.43	173.25	Ast + Eps
80	1.4076	1.4008	3.39	6.62	26.39	63.60	9.31	18.20	72.49	174.70	Ast + Eps
81	1.4141	1.4014	5.19	5.61	25.34	63.85	14.36	15.53	70.12	176.66	Ast + Eps
82	1.4196	1.4033	6.83	4.70	26.65	61.82	17.90	12.31	69.79	161.93	Db2 + Eps
83	1.4088	1.4028	8.04	4.44	26.03	61.50	20.88	11.52	67.59	159.71	Db2 + Eps
84, K	1.3924	1.4030	10.35	0.00	26.34	63.31	28.20	0.00	71.80	172.54	Ls + Eps
85	1.4008	1.4038	10.09	1.45	27.43	61.03	25.88	3.72	70.40	156.64	Ls + Eps
86	1.4138	1.4052	9.68	3.22	26.92	60.18	24.31	8.08	67.61	151.15	Ls + Eps
87, T₄	1.4315	1.4058	8.70	4.59	26.49	60.22	21.86	11.53	66.61	151.40	Ls + Eps + Db2
88, L	1.2933	1.3820	20.98	11.60	0.00	67.41	64.39	35.61	0.00	206.87	Ls + Db2
89	1.3062	1.3840	19.48	11.00	2.17	67.35	59.66	33.70	6.63	206.31	Ls + Db2
90	1.3173	1.3860	18.53	10.82	4.68	65.97	54.46	31.79	13.75	193.89	Ls + Db2
91	1.3314	1.3896	17.16	10.15	8.70	63.99	47.66	28.19	24.16	177.71	Ls + Db2
92	1.3500	1.3921	15.11	9.31	11.94	63.64	41.57	25.60	32.83	175.06	Ls + Db2
93	1.3675	1.3950	14.23	8.63	13.75	63.40	38.87	23.57	37.56	173.20	Ls + Db2
94	1.3868	1.3979	12.64	7.83	18.98	60.55	32.03	19.84	48.13	153.52	Ls + Db2
95	1.4061	1.4008	11.30	7.17	21.67	59.86	28.16	17.85	53.99	149.10	Ls + Db2
96	1.4111	1.4028	10.16	6.22	22.85	60.77	25.89	15.86	58.24	154.87	Ls + Db2
97	1.4233	1.4050	9.54	4.84	27.01	58.60	23.06	11.68	65.26	141.57	Ls + Db2

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