氯化铬和氯化镍浓度及其存在形式对ChCl-EG低共熔溶剂电导率的影响

doi:10.11949/0438-1157.20190060

摘要/Abstract

摘要：

研究了氯化铬(CrCl₃·6H₂O)和氯化镍(NiCl₂·6H₂O)浓度和存在形式对氯化胆碱-乙二醇(ChCl-EG)低共熔溶剂的黏度和电导率的影响。电喷雾质谱(ESI-MS)分析结果表明，在溶解有CrCl₃?6H₂O和NiCl₂?6H₂O 的ChCl-EG(ChCl-EG-NiCl₂·6H₂O-CrCl₃·6H₂O)溶液中出现了配阴离子[Cr(H₂O)₂Cl₄]^–和[Ni(H₂O)₂Cl₄]^2-。由此可以推断，Cr³⁺(或Ni²⁺)的两个d轨道、4s 和4p轨道发生d²sp³杂化，形成6个等同的杂化轨道，接受6个配体(Cl^-和H₂O)形成阴离子配合物。该溶液的电导率随温度的升高而增大，随总金属离子浓度的增大而减小。此外，溶液黏度随温度和总金属离子浓度的变化趋势与电导率相反。这主要是由于镍和铬配离子的形成改变了溶液中的离子组成。

关键词: 低共熔溶剂, 溶解, 存在形式, 电导率, 黏度, 配合物

Abstract:

The effects of existence form and total concentration of chromium chloride (CrCl₃·6H₂O) and nickel chloride (NiCl₂·6H₂O) on the conductivity and viscosity of choline chloride (ChCl)- ethylene glycol (EG) deep eutectic solvent were investigated. The ESI-MS analysis indicated that six-coordinated complexes are presented in the form of [Cr(H₂O)₂Cl₄]^- and [Ni(H₂O)₂Cl₄]^2-. It is deduced that the complex anions are formed through d²sp³ hybrid orbitals of Cr³⁺ (or Ni²⁺) ion and six d²sp³ hybrid orbitals are all filled with lone pair electrons which are donated by Cl^- and O atoms of H₂O, respectively. With the increase of temperature or decrease of total metal ions concentration, the electrical conductivity increases. In addition, the viscosity of the solution changes with temperature and total metal ion concentration as opposed to conductivity. This is mainly due to the formation of ions in the solution due to the formation of nickel and chromium complex ions.

Key words: deep eutectic solvent, dissolution, existence form, conductivity, viscosity, complexes

中图分类号:

TG 144

朱啸林, 徐存英, 唐杰, 华一新, 张启波, 刘海, 王祥, 黄梦婷. 氯化铬和氯化镍浓度及其存在形式对ChCl-EG低共熔溶剂电导率的影响[J]. 化工学报, 2019, 70(7): 2786-2794.

Xiaolin ZHU, Cunying XU, Jie TANG, Yixin HUA, Qibo ZHANG, Hai LIU, Xiang WANG, Mengting HUANG. Effects of existence form and concentrations of NiCl₂•6H₂O and CrCl₃•6H₂O on conductivity of ChCl-EG deep eutectic solvent[J]. CIESC Journal, 2019, 70(7): 2786-2794.

图/表 9

图1 ChCl-EG低共熔溶剂(a)和ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES(b)的负离子电喷雾质谱图，以及ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES的正离子电喷雾质谱图(c)

Fig.1 ESI-MS spectra of ChCl-EG DES (a) and ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES in negative ion mode(b)，and ESI-MS spectra of ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES (c) in positive ion mode

图2 总金属离子浓度和温度对ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES黏度的影响

Fig.2 Effect of temperature and total metal ion concentration (ctotal) on viscosity of ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES

图3 总金属离子浓度为400 mmol/L的ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES的黏度和电导率与温度的关系

Fig.3 Viscosity and electrical conductivity of ChCl-EG-NiCl2·6H2O-CrCl3·6H2O solution as function of temperature (ctotal=400 mmol/L)

图4 黏度对数(lnη)与温度倒数(T-1)的关系

Fig.4 Plot of logarithm of viscosity (lnη) against reciprocal value of absolute temperature (T-1)

图5 温度和总金属离子浓度对ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES电导率的影响

Fig.5 Effects of temperature and total metal ion concentration on conductivity of ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES

图6 不同温度下ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES的总金属离子浓度与其电导率的关系(a)，以及对(a)中数据的线性拟合(b)

Fig.6 Electrical conductivity of ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES as function of total metal ion concentration at different temperature(a), (b) is linear fitting of data shown in (a)

图7 ChCl-EG DES中(Ch+)、Cl-、[Cr(H2O)2Cl4]-和[Ni(H2O)2Cl4]2-的浓度与总金属离子浓度的关系

Fig.7 Concentration of Ch+ Cl-, [Cr(H2O)2Cl4]- and [Ni(H2O)2Cl4]2- as function of total metal ions concentration in ChCl-EG DES

图8 温度与浓度系数A和B的关系

Fig.8 Concentration coefficients A and B as function of temperature

表1 ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES电导活化能与总金属离子浓度的关系

Table 1 Relationship between conductance activation energy and total metal ion concentration of ChCl-EG-NiCl2·6H2O-CrCl3·6H2O DES

c_total/（mmol/L）	E_κ/（kJ/mol）
0	10.91
100	11.26
200	12.16
300	12.38
400	12.74
500	13.60

参考文献 38

1	曹玉鹏, 戴志强, 刘建涛,等. Ni-Cr合金层研究现状及展望[J]. 热加工工艺, 2017, 22(7): 29-32.
	CaoY P, DaiZ Q, LiuJ T, et al. Research status and prospect of Ni-Cr alloy layer[J]. Hot Working Technology, 2017, 22(7): 29-32.
2	张志. 氯化胆碱-乙二醇-三氯化铬低共熔体系中电沉积铬的研究[D]. 昆明: 昆明理工大学, 2014.
	ZhangZ. Study on electrodeposition of chromium in ChCl-EG-CrCl₃ eutectic system[D]. Kunming: Kunming University of Technology, 2014.
3	AghdamA S, AllahkaramS R, MahdaviS. Corrosion and tribological behavior of Ni-Cr alloy coatings electrodeposited on low carbon steel in Cr(Ⅲ)-Ni(Ⅱ) bath[J]. Surf. Coat. Technol., 2015, 281: 144-149.
4	SurvilienėS, ČešūnienėA, JasulaitienėV, et al. The use of XPS for study of the surface layers of CrNi alloys electrodeposited from the Cr(Ⅲ)+Ni(Ⅱ) bath[J]. Appl. Surf. Sci., 2012, 258: 9902-9906.
5	王茂全. 化学方法处理电镀废水[J]. 中国资源综合利用, 2018, 375(2): 55-57.
	WangM Q. Chemical treatment of electroplating wastewater[J]. China Resources Comprehensive Utilization, 2018, 375(2): 55-57.
6	李冰, 严琪, 宋皓. 喷射电沉积制备替代六价铬的三价铬镀层[J]. 机械工程师, 2018, 327(9): 50-52.
	LiB, YanQ, SongH. Trivalent chromium coatings prepared by jet electrodeposition to replace the hexavalent chromium[J]. Mechanical Engineer, 2018, 327(9): 50-52.
7	GenganS, SubramanianM. Electrodeposition of Fe-Ni-Cr alloy from deep eutectic system containing choline chloride and ethylene glycol[J]. Int. J. Electrochem. Sci., 2011, 6: 1468-1478.
8	SurvilieneS, Lisowska-OleksiakA, SelskisA, et al. Corrosion behaviour of Cr coatings deposited from Cr(Ⅲ) formate-urea electrolytes[J]. Trans. IMF, 2006, 84: 241-245.
9	SrimathiS N, MayannaS M. Electroplating of thin films of magnetic FeNi alloys[J]. Materials Chemistry and Physics, 1984, 11: 351-364.
10	苏波, 张贤杰, 李坚,等. CH₃CONH₂-EG低共熔溶剂的物化性质[J]. 昆明理工大学学报(自然科学版), 2017, 3(2):16-21+52.
	SuB, ZhangX J, LiJ, et al. Physicochemical properties of CH₃CONH₂-EG deep eutectic solvents[J]. Journal of Kunming University of Science and Technology (Natural Science Edition), 2017, 3(2): 16-21+52.
11	雷震, 徐存英, 卢东辉,等. 低共熔溶剂处理含锌烟尘的研究[J]. 有色金属(冶炼部分), 2017, 8(2): 5-8.
	LeiZ, XuC Y, LuD H, et al. Study on treatment of zinc dust with deep eutectic solvent[J]. Nonferrous Metals (Extractive Metallurgy), 2017, 8(2): 5-8.
12	张盈盈, 陆小华, 冯新, 等. 胆碱类低共熔溶剂的物性及应用[J]. 化学进展, 2013, 25(6): 881-892.
	ZhangY Y, LuX H, FengX, et al. Physical properties and application of choline eutectic solvents[J]. Progress in Chemical, 2013, 25(6): 881-892.
13	HuoC, ChanT H. A novel liquid-phase strategy for organic synthesis using organic ions as soluble supports[J]. Chemical Society Reviews, 2010, 39(8): 2977-3006.
14	YangL, LiuY E, Zu, et al. Optimize the process of ionic liquid-based ultrasonic-assisted extraction of aesculin and aesculetin from Correx fraxini by response surface methodology[J]. Chemical Engineering Journal, 2011, 175(1): 539-547.
15	LiZ, FriedrichA, TaubertA. Gold microcrystal synthesis via reduction of HAuCl₄ by cellulose in the ionic liquid 1-butyl-3-methyl imidazolium chloride[J]. Journal of Materials Chemistry, 2008, 18(9): 1008-1014.
16	方园, 魏琦峰, 任秀莲,等. 低共熔溶剂中电化学沉积的研究进展[J]. 电镀与精饰, 2015, 37(10): 12-17.
	FangY, WeiQ F, RenX L, et al. Advances in electrochemical deposition in low eutectic solvents[J]. Plating & Fishing, 2015, 37(10): 12-17.
17	AbbottA P, CapperG, DaviesD L, et al. Electrodeposition of chromium black from ionic liquids[J]. Transactions of the IMF, 2004, 82(1/2): 14-17.
18	AbbottA P, Al-BarzinjyA A, AbbottP D, et al. Speciation, physical and electrolytic properties of eutectic mixtures based on CrCl₃·6H₂O and urea[J]. Physical Chemistry Chemical Physics, 2014, 16(19): 9047-9055.
19	ZhangQ, VigierK D O, RoyerS, et al. Deep eutectic solvents: syntheses, properties and applications[J]. Chemical Society Reviews, 2012, 41(21): 7108-7146.
20	AbbottA P, CapperG, DaviesD L, et al. Selective extraction of metals from mixed oxide matrixes using choline-based ionic liquids[J]. Inorganic Chemistry, 2005, 44(19): 6497-6499.
21	ZouY, XuH, WuG, et al. Structural analysis of [ChCl]_m[ZnCl₂]_n ionic liquid by X-ray absorption fine structure spectroscopy[J]. The Journal of Physical Chemistry B, 2009, 113(7): 2066-2070.
22	LinI J B, VasamC S. Metal-containing ionic liquids and ionic liquid crystals based on imidazolium moiety[J]. Journal of Organometallic Chemistry, 2005, 690(15): 3498-3512.
23	AbbottA P, CapperG, DaviesD L, et al. Solubility of metal oxides in deep eutectic solvents based on choline chloride[J]. Journal of Chemical & Engineering Data, 2006, 51(4): 1280-1282.
24	VorobievaS N, BaidinaI A, BelyaevA V, et al. Crystal structure of [Rh(H₂O)₅Cl] (C₇H₇O₃S)₂ and Cs[Rh(H₂O)₅NO₃] (C₇H₇O₃S)₃·H₂O[J]. Journal of Structural Chemistry, 2015, 56(8): 1606-1612.
25	MccalmanD C, SunL, ZhangY, et al. Speciation, conductivities, diffusivities, and electrochemical reduction as a function of water content in mixtures of hydrated chromium chloride/ choline chloride[J]. Journal of Physical Chemistry B, 2015, 119(19): 6018-6023.
26	ShupackS I. The chemistry of chromium and some resulting analytical problems[J]. Environmental Health Perspectives, 1991, 92: 7-11.
27	AbbottA P, GlenC, DaviesD L, et al. Ionic liquid analogues formed from hydrated metal salts[J]. Chemistry - A European Journal, 2010, 10(15): 3769-3774.
28	ElvingP J, ZemelB. Absorption in the ultraviolet and visible regions of chloroaquochromium(Ⅲ) ions in acid media[J]. Journal of the American Chemical Society, 1957, 79(6): 1281-1285.
29	AbbottA P, CapperG, DaviesD L, et al. Novel ambient temperature ionic liquids for zinc and zinc alloy electrodeposition[J]. Transactions of the IMF, 2001, 79(6): 204-206.
30	AbbottA P, DavidB, GlenC, et al. Deep eutectic solvents formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids[J]. Journal of the American Chemical Society, 2004, 126(29): 9142-9147.
31	ParkerJ F, CheekG T, RoeperD F, et al. Electronic absorption and voltammetric analysis of Ni(Ⅱ) coordination in the room temperature ionic liquid: 1-ethyl-3-Methylimidizolium chloride/aluminum chloride[J]. ECS Transactions, 2012, 41(36): 23-33.
32	华一新. 冶金动力学导论[M]. 北京: 冶金工业出版社, 2004: 27-29.
	HuaY X. Introduction to Metallurgical Dynamics[M]. Beijing: Metallurgical Industry Press, 2004: 27-29.
33	刘春萍, 刘刚, 胡玉才, 等. 1-苄基-4-甲基吡啶盐离子液体的合成及其电导性能的研究[J]. 石油化工, 2011, 40(7): 764-769.
	LiuC P, LiuG, HuY C, et al. Synthesis and electric conductivity of 1-benzyl-4-methylpyridine ionic liquids[J]. Petrochemical Technology, 2011, 40(7): 764-769.
34	何志强, 鄢浩, 王骑虎,等. 温度对氯化胆碱/多元醇型低共熔溶剂物性的影响[J]. 上海大学学报(自然科学版), 2015, 21(3): 384-392.
	HeZ Q, YanH, WangQ H, et al. Effect of temperature on physic-chemical properties of deep eutectic solvent based on choline chloride and polyols[J]. Journal of Shanghai University (Natural Science Edition), 2015, 21(3): 384-392.
35	王喜然, 华一新, 赵秋凝, 等. AlCl3-BMIC 离子液体率 [J]. 中国有色金属学 2006, 16 (12): 2138-2141.
	WangX R, HuaY X, ZhaoQ N, et al. Electrical conductivity of AlCl₃-BMIC room temperature ionic liquids[J]. The Chinese Journal of Nonferrous Metals, 2006, 16 (12): 2138-2141.
36	雷震，徐存英，华一新，等. ChCl-urea-ZnO低共熔溶剂体系的电化学行为[J]. 化工学报, 2017, 68(8): 3301-3309.
	LeiZ, XuC Y, HuaY X, et al. Eelectrochemical behaviors of ZnO in choline chloride-urea deep eutectic solvents[J]. CIESC Journal, 2017, 68(8): 3301-3309.
37	高颖, 邬冰. 电化学基础[M]. 北京: 化学工业出版社, 2004: 11-14.
	GaoY, WuB. Foundations of Electrochemistry[M]. Beijing: Chemical Industry Press, 2004: 11-14.
38	AbbottA P, CapperG, MckenzieK J, et al. Electrodeposition of zinc-tin alloys from deep eutectic solvents based on choline chloride[J]. Journal of Electroanalytical Chemistry, 2007, 599(2): 288-294.

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