六水氯化镁在六种多元醇中溶解度的测定和关联

doi:10.19964/j.issn.1006-4990.2021-0097

Abstract

Abstract:

Solubility of magnesium chloride hexahydrate is an important basic data in comprehensive utilization of magnesium salts.The static equilibrium method was used to determine the content of magnesium chloride hexahydrate in 1,2-propanedi-ol,1,3-propanediol,1,3-butanediol,diethylene glycol,triethylene glycol,and dipropylene glycol（278.15~328.15 K）.The experimental results showed that the solubility of magnesium chloride hexahydrate in six polyols increased with the increase of temperature,among which the solubility of diethylene glycol was the largest,and the solubility of diethylene glycol changed more obviously with temperature than other polyols.The Apelblat equation,λh equation,Van′t Hoff equation and polynomial equation were used to correlate the solubility data,and the results were good.Among them,the fitting results of Apelblat equa-tion and polynomial equation were better than other equations.The Van′t Hoff equation was used to calculate the dissolution enthalpy,dissolution entropy and Gibbs free energy of the six systems.These results had important reference value for the separation and extraction of magnesium salts and the preparation of magnesium-based functional materials.

Key words: magnesium chloride hexahydrate, polyols, solubility, solubility model

CLC Number:

TQ132.2

CHEN Yunfei,MAO Lili,LIU Dan,WANG Haizeng. Measurement and correlation of solubility of magnesium chloride hexahydrate in six polyols[J]. Inorganic Chemicals Industry, 2021, 53(12): 85-90.

Figures/Tables 8

Table 1

Fig.1

Fig.2

Table 2

Table 3

Table 4

Table 5

Table 6

References 38

[1]	张景红, 周启立, 张向怡. 卤水中氧化镁的提取工艺进展[J]. 无机盐工业, 2010, 42(8):7-9.
[2]	HOU X H, ZHENG N P. An insight on future development approach- es of salt lake magnesium resources:From the current situation of China′s magnesium industry[J]. Acta Geologica Sinica, 2015, 88(s1):335-336. doi: 10.1111/1755-6724.12279_12
[3]	ZHANG Z, LU X, WANG T, et al. The dehydration of MgCl₂·6H₂O in MgCl₂·6H₂O-KCl-NH₄Cl system[J]. Journal of Analytical and App- lied Pyrolysis, 2014, 110:248-253.
[4]	KIM I T, YAMABUKI K, SUMIMOTO M, et al. Characteristics of tetrahydrofuran-based electrolytes with magnesium alkoxide addi- tives for rechargeable magnesium batteries[J]. Journal of Power So- urces, 2016, 323:51-56.
[5]	ZHENG T X, HU Y B, PAN F S, et al. Fabrication of corrosion-re- sistant superhydrophobic coating on magnesium alloy by one-step electrodeposition method[J]. Journal of Magnesium and Alloys, 2019, 7(2):193-202. doi: 10.1016/j.jma.2019.05.006
[6]	HE F, LU T, FANG X, et al. Effects of strontium amount on the me- chanical strength and cell-biological performance of magnesium- strontium phosphate bioceramics for bone regeneration[J]. Materi- als Science and Engineering:C, 2020, 112.Doi: 10.1016/j.msec.2020.110892. doi: 10.1016/j.msec.2020.110892
[7]	ZHOU H, LI J, LI J, et al. Calcium phosphate coating on biomedical WE43 magnesium alloy pretreated with a magnesium phosphate la- yer for corrosion protection[J]. Surface and Coatings Technology, 2020, 401.Doi: 10.1016/j.surfcoat.2020.126248. doi: 10.1016/j.surfcoat.2020.126248
[8]	LAN Z, LU Y C. Tailoring morphology and bulk density of magnesi- um ethoxide particles by adding n-hexane and silicone oil[J]. Par- ticuology, 2020, 53:168-174.
[9]	ZHANG D M, HUANG J F, GANG T M. The dehydration of magne- sium chloride by butanol distillation[J]. Journal of Central-South Institute of Mining and Metallurgy, 1988, 19(4):388-394.
[10]	崔振华. 六水氯化镁在乙二醇中的溶解结晶行为研究[D]. 西宁:中国科学院青海盐湖研究所, 2014.
[11]	屈俊. 六水氯化镁在乙二醇中的溶解结晶行为[J]. 化工设计通讯, 2019, 45(6):126-128,130.
[12]	刘丹, 毛丽莉, 王海增. 六水氯化镁在醇类溶剂中溶解度的测定与关联[J]. 高校化学工程学报, 2018, 32(1):24-29.
[13]	刘丹, 毛丽莉, 王海增. 非水体系中制备三水磷酸氢镁:中国, 107055500A[P]. 2017-08-18.
[14]	LIU D, MAO L L, WANG H Z. Preparation of uniform nerberyite crystal in nonaqueous system[J]. Materials Letters, 2019, 240:169-171. doi: 10.1016/j.matlet.2019.01.016
[15]	GAMBE J, JOUIN J, REMONDIERE F, et al. Solvent effect in the nonaqueous synjournal of ZrO₂ nanoparticles under alkaline condi- tions[J]. Journal of Materials Science, 2020, 55(7):2802-2814. doi: 10.1007/s10853-019-04137-9
[16]	杨红, 金达莱, 马照军, 等. 醇类添加剂对碳酸钙形貌及晶型的影响[J]. 浙江理工大学学报, 2007(5):549-552.
[17]	靳苗苗. 二氧六环与氯化镁络合反应结晶及热分解过程研究[D]. 上海:华东理工大学, 2015.
[18]	陆慕瑶. 三种苯乙酸类和一种酮类物质的固液相平衡研究[D]. 北京:北京化工大学, 2018.
[19]	黄琼珠, 路贵民, 汪瑾, 等. MgCl₂·6H₂O热分解机理的研究[J]. 无机材料学报, 2010, 25(3):306-310. doi: 10.3724/SP.J.1077.2010.00306
[20]	中国科学院青海盐湖研究所分析室. 卤水和盐的分析方法[M]. 北京: 科学出版社, 1988.
[21]	饶念, 魏立安. 活性炭废水中钙镁离子含量测定方法研究[J]. 江西科学, 2011, 29(5):579-582.
[22]	IRFAN M, WANG Y M, XU T W. Novel electrodialysis membranes with hydrophobic alkyl spacers and zwitterion structure enable high monovalent/divalent cation selectivity[J]. Chemical Engineering Journal, 2020, 383.Doi: 10.1016/j.cej.2019.123171. doi: 10.1016/j.cej.2019.123171
[23]	LI Z L, WANG Z R, LI M Y, et al. Measurement and correlation of solubility of methyl gallate in nine pure and ethanol+n-propanol mixed solvents at temperatures within 293.15-333.15 K[J]. Jour- nal of Molecular Liquids, 2019, 293.Doi: 10.1016/j.molliq.2019.111531. doi: 10.1016/j.molliq.2019.111531
[24]	JI W, MENG Q, LI P, et al. Measurement and correlation of the so- lubility of p-coumaric acid in nine pure and water+ethanol mixed solvents at temperatures from 293.15 to 333.15 K[J]. Journal of Chemical & Engineering Data, 2016, 61(10):3457-3465. doi: 10.1021/acs.jced.6b00361
[25]	李涛, 沙娇, 赵瑞, 等. 双季戊四醇在3种混合溶剂中的固-液相平衡[J]. 化工学报, 2020, 71(1):245-253.
[26]	APELBLAT A, MANZUROL E. Solubilities ofo-acetylsalicylic,4- aminosalicylic,3,5-dinitrosalicylic,andp-toluic acid,and magne- sium-DL-aspartate in water from T=(278 to 348) K[J]. The Jo- urnal of Chemical Thermodynamics, 1999, 31(1):85-91.
[27]	陈丽芳, 张勤勤, 林田, 等. 硼酸在氯化钙溶液中溶解度的测定与关联[J]. 无机盐工业, 2019, 51(5):70-73.
[28]	WANG M, LIU Y, DU S, et al. Determining the solubility and un- derstanding the solid-liquid equilibrium behavior of cyhalothric acid in eleven pure solvents[J]. Journal of Molecular Liquids, 2020, 300.Doi: 10.1016/j.molliq.2019.112365. doi: 10.1016/j.molliq.2019.112365
[29]	BUCHOWSKI H, KSIAZCZAK A, PIETRZYK S. Solvent activity along a saturation line and solubility of hydrogen-bonding solids[J]. The Journal of Physical Chemistry, 1980, 84(9):975-979. doi: 10.1021/j100446a008
[30]	WU Y F, WU Y C, ZHANG X L. The dissolution behavior and ap- parent thermodynamic analysis of propacetamol hydrochloride in pure and mixed solvents[J]. The Journal of Chemical Thermodyna- mics, 2020, 143.Doi: 10.1016/j.jct.2019.106018. doi: 10.1016/j.jct.2019.106018
[31]	LI D, CAO D L, CHEN L Z, et al. Solubility of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate in(formic acid,water) and their binary solvents from 298.15 K to 333.15 K at 101.1 kPa[J]. The Journal of Chemical Thermodynamics, 2019, 128:10-18. doi: 10.1016/j.jct.2018.07.030
[32]	张莉媛, 王刚, 齐美玲, 等. 表面活性剂对光卤石中氯化钾结晶介稳区和诱导期的影响[J]. 无机盐工业, 2020, 52(6):46-49.
[33]	XIAO M, LIU H, WANG J, et al. An experimental and modeling study of physical N₂O solubility in 2-(ethylamino) ethanol[J]. The Journal of Chemical Thermodynamics, 2019, 138:34-42. doi: 10.1016/j.jct.2019.06.008
[34]	WONGKAEW K, FULAJTAROVA K, HRONEC M, et al. Measu- rement of the solubility of the salt of 2-mercaptobenzothiazole with cyclohexylamine and tert-butylamine in various solvents at low temperatures:Models and thermodynamic parameters[J]. Fluid Ph- ase Equilibria, 2017, 434:141-151.
[35]	GUO H, CAO D, LIU Y, et al. Determination and correlation of so- lubility of N-methyl-3,4,5-trinitropyrazole(MTNP) in ten pure solvents from 283.15 K to 323.15 K[J]. Fluid Phase Equilibria, 2017, 444:13-20. doi: 10.1016/j.fluid.2017.04.008
[36]	LI R, YIN X, ZHANG J, et al. Improving the solubility of temozolo- mide by cosolvent and its correlation with the Jouyban-Acree and CNIBS/RK models[J]. The Journal of Chemical Thermodynamics, 2019, 139.Doi: 10.1016/j.jct.2019.07.017. doi: 10.1016/j.jct.2019.07.017
[37]	谢永, 蒋奇齐, 王红艳, 等. 对二甲氨基苯甲醛在不同的溶剂中溶解度测定与关联[J]. 高校化学工程学报, 2017, 31(2):284-290.
[38]	ZHANG Y, GUO F, CUI Q, et al. Measurement and correlation of the solubility of vanillic acid in eight pure and water+ethanol mixed solvents at temperatures from(293.15 to 323.15) K[J]. Journal of Chemical & Engineering Data, 2016, 61(1):420-429. doi: 10.1021/acs.jced.5b00619

T/K	x₁
T/K	1,2-丙二醇	1,3-丙二醇	1,3-丁二醇	一缩二乙二醇	二缩三乙二醇	一缩二丙二醇
278.15	0.369 6	0.386 1	0.356 8	0.436 1	0.390 8	0.304 2
283.15	0.379 6	0.400 2	0.364 7	0.446 4	0.404 5	0.312 8
288.15	0.388 5	0.412 4	0.374 1	0.453 2	0.422 1	0.325 7
293.15	0.397 1	0.426 2	0.383 9	0.465 8	0.437 9	0.338 6
298.15	0.405 3	0.438 1	0.396 9	0.478 9	0.453 6	0.352 3
303.15	0.414 2	0.451 1	0.404 1	0.487 7	0.475 6	0.365 9
308.15	0.425 8	0.462 1	0.414 9	0.502 2	0.492 5	0.378 5
313.15	0.436 2	0.473 9	0.425 8	0.513 1	0.516 8	0.392 1
318.15	0.443 5	0.488 3	0.440 9	0.522 8	0.535 7	0.406 8
323.15	0.453 4	0.496 3	0.452 5	0.532 1	0.557 8	0.421 4
328.15	0.465 7	0.512 9	0.465 2	0.545 3	0.583 9	0.441 3

溶剂	A₁	B₁	C₁	RAD/%
1,2-丙二醇	-15.463	302.639	2.378	0.211 6
1,3-丙二醇	3.566	-628.692	-0.401	0.210 0
1,3-丁二醇	-33.525	1 053.395	5.101	0.200 3
一缩二乙二醇	-9.321	35.018	1.486	0.280 0
二缩三乙二醇	-43.786	1 311.884	6.775	0.224 2
一缩二丙二醇	-32.099	821.602	4.966	0.275 7
平均值	—	—	—	0.274 6

溶剂	λ	h	RAD/%
1,2-丙二醇	-0.494	3 369.724	0.742 9
1,3-丙二醇	-0.429	2 422.762	0.940 4
1,3-丁二醇	-0.417	3 143.828	0.496 6
一缩二乙二醇	-0.592	2 273.479	0.752 6
二缩三乙二醇	0.007	1 446.312	0.275 2
一缩二丙二醇	-0.217	3 031.885	0.601 6
平均值	—	—	0.616 2

溶剂	A₂	B₂	RAD/%
1,2-丙二醇	0.501	-417.152	0.303 2
1,3-丙二醇	0.875	-507.305	0.220 3
1,3-丁二醇	0.724	-491.524	0.544 9
一缩二乙二醇	0.655	-414.808	0.324 9
二缩三乙二醇	1.717	-743.853	0.702 4
一缩二丙二醇	1.256	-684.774	0.495 9
平均值	—	—	0.473 2

溶剂	A₃	B₃	C₃	D₃	RAD/%
1,2-丙二醇	6.822	-5.860	0.019	-1.733	0.189 1
1,3-丙二醇	1.935	0.000	0.057	-5.881	0.161 2
1,3-丁二醇	6.200	-4.647	0.013	-1.061	0.213 7
一缩二乙二醇	-2.852	0.000	-0.077	7.878	0.301 0
二缩三乙二醇	2.284	-3.837	-0.002	0.548	0.223 0
一缩二丙二醇	1.242	0.000	0.030	-2.897	0.280 3
平均值	—	—	—	—	0.258 8

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Measurement and correlation of solubility of magnesium chloride hexahydrate in six polyols

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 38

Related Articles 15

Metrics

Comments

Recommended 0

溶剂	ΔH_sol^o / （J·mol^-1）	ΔS_sol^o / （J·mol^-1·K^-1）	ΔG_sol^o / （J·mol^-1）	ξ_H /%	ξ_TS /%
1,2-丙二醇	3 468.19	4.16	2 211.90	73.41	26.59
1,3-丙二醇	4 217.69	7.30	2 010.81	65.65	34.35
1,3-丁二醇	4 086.50	6.03	2 262.17	69.14	30.86
一缩二乙二醇	3 448.73	5.42	1 809.73	67.79	32.21
二缩三乙二醇	6 184.37	14.30	1 860.00	58.85	41.15
一缩二丙二醇	5 693.18	10.52	2 513.52	64.16	35.84

[1]	FENG Xia, YU Xuefeng, YAO Zhihao, LUO Jun, REN Siying, ZHAO Zhixing, YU Xudong. Study on phase equilibria of aqueous ternary system of Na⁺（Mg²⁺），Ca²⁺∥Cl^--H₂O at 278.2 K [J]. Inorganic Chemicals Industry, 2024, 56(1): 47-52.
[2]	DENG Wenqing,ZHU Jing,FAN Xiaojuan,CHEN Yan,LI Tianxiang. Phase equilibria of ternary system of KH₂PO₄-（NH₂）₂CO-H₂O at 313.15 K [J]. Inorganic Chemicals Industry, 2023, 55(1): 100-105.
[3]	LI Yan,WANG Yansong,CHENG Huaigang,KANG Jin,LI Enze,LÜ Hongzhou,LIU Qian. Rapid quality inspection of high-purity lithium carbonate based on determination of magnesium by water-soluble probe method [J]. Inorganic Chemicals Industry, 2023, 55(1): 87-92.
[4]	CHEN Shuai,YANG Bo,CHEN Niancu,LUO Jun,REN Siying,ZENG Ying,YU Xudong. Study on phase equilibria of ternary system NH₄Cl+MgCl₂+H₂O at 323.2 K [J]. Inorganic Chemicals Industry, 2022, 54(4): 100-103.
[5]	MA Yujun,WANG Xiao,LI Shuya,ZHANG Fukang,LI Juan. Phase equilibria of quaternary system of NaCl+NaBO₂+Na₂CO₃+H₂O at 298.15 K [J]. Inorganic Chemicals Industry, 2022, 54(10): 42-46.
[6]	ZHANG Huanhuan,CHENG Zhuo,TANG Xiuhua,ZHANG Fengzhen. Determination and correlation of solubility of potassium dihydrogen phosphate in acetonitrile-water solvent [J]. Inorganic Chemicals Industry, 2022, 54(1): 83-85.
[7]	Wang Bin,Deng Xiaochuan,Shi Yifei,Dong Chaochao,Fan Faying,Zhu Chaoliang,Fan Jie. Online determination of the solubility of lithium carbonate in water and NaCl-KCl solution system [J]. Inorganic Chemicals Industry, 2021, 53(7): 73-79.
[8]	Yang Jiamin,Zhu Jing,Hu Xue,Wu Qiang,Li Tianxiang. Determination and correlation for solid-liquid phase equilibrium of ternary KCl-NH₄Cl-H₂O and KH₂PO₄-NH₄H₂PO₄-H₂O systems at 283.15 K [J]. Inorganic Chemicals Industry, 2021, 53(1): 30-35.
[9]	Liu Juexin,Zheng Chenggang,Ye Shichao. Determination and application of thermodynamic data of potassium dihydrogen phosphate crystal [J]. Inorganic Chemicals Industry, 2021, 53(1): 62-64.
[10]	Zhang Liyuan,Wang Gang,Qi Meiling,Xie Yulong. Effect of surfactants on metastable zone and induction period of KCl crystals in carnallite [J]. Inorganic Chemicals Industry, 2020, 52(6): 46-49.
[11]	Wang Jukui,Dong Xingfeng,Zhao Dong,Wang Shiqiang,Guo Yafei,Deng Tianlong. Solid-liquid phase equilibria in quaternary system lithium borate-potassium borate-magnesium borate-water at 308.15 K [J]. Inorganic Chemicals Industry, 2020, 52(5): 27-30.
[12]	Qi Meiling,Wang Gang,Zhang Liyuan,Xie Yulong. Determination of KCl solubility,interfacial region and induction period in carnallite [J]. Inorganic Chemicals Industry, 2020, 52(5): 45-49.
[13]	Wang Yubin,Wang Wangbo,Zhu Xinfeng,Xun Jingwen,Dang Weiben. Effect of different magnesium salts on solubility behavior of calcium carbonate under magnetization [J]. Inorganic Chemicals Industry, 2020, 52(3): 35-38.
[14]	Wu Qiang,Hu Xue,Zhu Jing,Yang Jiamin,Li Tianxiang. Phase equilibrium of KH₂PO₄-KCl-H₂O and NH₄H₂PO₄-NH₄Cl-H₂O ternary system at 283.15 K [J]. Inorganic Chemicals Industry, 2020, 52(11): 24-28.
[15]	Cao Peng. Effect of acid soluble main reverse on solubility of solid phase of titanium white production by sulfuric acid process [J]. Inorganic Chemicals Industry, 2019, 51(9): 54-56.