拉曼光谱法研究Na+,Mg2+//SO42-, Cl-, H2O四元体系中SO42-离子缔合结构特征及其变化规律

引用本文: 阎波, 周桓, 李文轩. 拉曼光谱法研究Na⁺,Mg²⁺//SO₄^2-, Cl^-, H₂O四元体系中SO₄^2-离子缔合结构特征及其变化规律[J]. 物理化学学报, 2016, 32(2): 405-414. doi: 10.3866/PKU.WHXB201511192 shu

Citation: YAN Bo, ZHOU Huan, LI Wen-Xuan. Studies on the Characteristics and Behaviors of the Ion Association Structures of SO₄^2- in Na⁺,Mg²⁺//SO₄^2-, Cl^-,H₂O System by Raman Spectroscopy[J]. Acta Physico-Chimica Sinica, 2016, 32(2): 405-414. doi: 10.3866/PKU.WHXB201511192 shu

拉曼光谱法研究Na⁺,Mg²⁺//SO₄^2-, Cl^-, H₂O四元体系中SO₄^2-离子缔合结构特征及其变化规律

阎波 ^1, ,
周桓 ^{2,
,} ,
李文轩 ^2,

1.
1 天津科技大学海洋与环境学院, 天津市海洋资源与化学重点实验室, 天津 300457;
2.
2 天津科技大学化工与材料学院, 天津市海洋资源与化学重点实验室, 天津 300457

通讯作者: 周桓

基金项目:
国家自然科学基金(21176189,U1407204) (21176189,U1407204)

天津市应用基础与前沿技术研究计划(15JCYBJC23200) (15JCYBJC23200)

教育部科研创新团队培育计划([2013]373) ([2013]373)

天津市高等学校创新团队培养计划(TD12-5004)资助项目 (TD12-5004)

摘要: 复杂水盐体系存在稳态和介稳固液相平衡以及复杂的成盐规律。为了解固液平衡状态下液相的结构特征,本文采用拉曼光谱技术并结合高斯-洛伦兹去卷积分峰拟合程序对Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O四元体系及其二元和三元子体系中ν₁-SO₄^2-的离子缔合结构特征进行了分析。研究结果表明:SO₄^2-在Na₂SO₄-H₂O体系存在自由态SO₄^2-和SO₄^2-离子簇两种结构,在MgSO₄-H₂O,MgSO₄-MgCl₂-H₂O及Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O等含镁体系中,还有Mg²⁺-H₂O-SO₄^2-和Mg²⁺-OSO₃^2-两种缔合结构。在二元和三元体系中ν₁-SO₄^2-的离子缔合结构以自由态SO₄^2-为主,随着SO₄^2-离子总浓度的变化,上述四种结构所占比例会发生规律性变化。Na⁺,Mg²⁺//SO₄^2-, Cl^-, H₂O四元体系在NaCl减少及等温蒸发过程中,自由态SO₄^2-结构比例逐步降低,Mg²⁺和SO₄^2-相结合形成Mg²⁺-H₂O-SO₄^2-或Mg²⁺-OSO₃^2-结构的机会增多,在复盐区还会形成SO₄^2-离子簇结构。由此判断溶液结构的适应性变化是导致介稳现象的重要原因。进一步的相关分析表明:SO₄^2-的浓度和耶涅克指数J 与ν₁-SO₄^2-峰的峰强度和峰面积存在正相关关系,Mg²⁺浓度是影响ν₁-SO₄^2-峰中四种缔合结构的比例发生变化的主要因素。

关键词:

English

Studies on the Characteristics and Behaviors of the Ion Association Structures of SO₄^2- in Na⁺,Mg²⁺//SO₄^2-, Cl^-,H₂O System by Raman Spectroscopy

YAN Bo ^1, ,
ZHOU Huan ^{2,
,} ,
LI Wen-Xuan ^2,

1.
1 Tianjin Key Laboratory of Marine Resource and Chemistry, College of Marine and Environmental Sciences, Tianjin University of Science & Technology, Tianjin 300457, P. R. China;
2.
2 Tianjin Key Laboratory of Marine Resource and Chemistry, College of Chemical Engineering and Materials Sciences, Tianjin University of Science & Technology, Tianjin 300457, P. R. China

Corresponding author: 周桓

Received Date: 27 July 2015
Fund Project:
国家自然科学基金(21176189,U1407204)

天津市应用基础与前沿技术研究计划(15JCYBJC23200)

教育部科研创新团队培育计划([2013]373)

天津市高等学校创新团队培养计划(TD12-5004)资助项目

Abstract: Stable and metastable solid-liquid equilibria phenomena and complex salt-forming behaviors exist in complex salt-water systems. To realize the relationship between salt-forming behavior and liquid structure, the characteristics of ion association structures of SO₄^2- in Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O system and its binary, ternary subsystems were studied by Raman spectroscopy, combined with a Gauss-Lorentz peak fitting program. The spectrum experimental results show that there were two ion association structures of SO₄^2- as non-associated SO₄^2- and SO₄^2- groups in the Na₂SO₄-H₂O system, while in the MgSO₄-H₂O, MgSO₄-MgCl₂-H₂O, and Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O systems, there were also Mg²⁺-H₂O-SO₄^2- and Mg²⁺-OSO₃^2- structures. Non-associated SO₄^2- was the main structure in the ν₁-SO₄^2- band of binary (MgSO₄ Na₂SO₄) and ternary (MgSO₄-MgCl₂-H₂O) subsystems, and with varying SO₄^2- concentration, these four types of SO₄^2- ion association structure varied regularly. Likewise, the ion association structures of SO₄^2- in the Na⁺, Mg²⁺//SO₄^2-, Cl^-, H₂O system changed regularly during both the processes of NaCl crystallization and isothermal evaporation. This was evident when, during the process of decreasing NaCl concentration and increasing MgSO₄, the content of non-associated SO₄^2- decreased, the chance of Mg²⁺-H₂O-SO₄^2- and Mg²⁺-OSO₃^2- structure formation increased, and the SO₄^2- group structure appeared in the astrachanite region. More importantly, the adaptive changes in solution structure during the progress of evaporation can result in the appearance of metastable phenomena. Further linear analysis showed that the concentration and Jänecke index (J) value of SO₄^2- were positively related to the intensity and peak area of the ν₁-SO₄^2- band, and the concentration of Mg²⁺ affected the contents of four ion association structures in the ν₁-SO₄^2- band mainly.

Key words:

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拉曼光谱法研究Na⁺,Mg²⁺//SO₄^2-, Cl^-, H₂O四元体系中SO₄^2-离子缔合结构特征及其变化规律

通讯作者: 周桓

English

Studies on the Characteristics and Behaviors of the Ion Association Structures of SO₄^2- in Na⁺,Mg²⁺//SO₄^2-, Cl^-,H₂O System by Raman Spectroscopy

Corresponding author: 周桓

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