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

摘要/Abstract

摘要：

六水氯化镁的溶解度是镁盐综合利用的重要基础数据。采用静态平衡法测定了六水氯化镁在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6种多元醇中的溶解度（278.15~328.15 K）。实验结果表明,六水氯化镁在6种多元醇中的溶解度均随着温度的升高而增大,其中在一缩二乙二醇中的溶解度最大,在二缩三乙二醇中的溶解度随着温度的变化较其他多元醇变化更为明显。使用Apelblat方程、λh方程、Van′t Hoff方程和多项式方程对溶解度数据进行了关联,结果良好,其中Apelblat方程和多项式方程拟合结果优于其他方程。利用Van′t Hoff方程计算了6种体系的溶解焓、溶解熵和吉布斯自由能。这些结果对镁盐的分离提取及镁基功能材料的制备具有重要的参考价值。

关键词: 六水氯化镁, 多元醇, 溶解度, 溶解度模型

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

中图分类号:

TQ132.2

陈云飞,毛丽莉,刘丹,王海增. 六水氯化镁在六种多元醇中溶解度的测定和关联[J]. 无机盐工业, 2021, 53(12): 85-90.

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.

图/表 8

表1

图1

图2

表2

表3

表4

表5

表6

参考文献 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

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会