Density Functional Theory of Molecular Structure and Properties of Fatty Acid Collectors
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摘要:
这是一篇矿物加工工程领域的论文。脂肪酸类捕收剂广泛应用于浮选氧化矿，其分子结构是影响浮选性能的重要因素，为了从微观角度揭示脂肪酸捕收剂结构变化对其反应活性的影响，采用密度泛函理论研究了脂肪酸电子结构与性能的关系。研究结果表明：油酸分子和油酸根离子中氧原子有很强的反应活性，氧原子是油酸与氧化矿物表面作用的键合原子；油酸根离子的两个氧原子具有相近的化学活性，且在费米能级处的态密度大于油酸分子，使得油酸根离子的活性明显强于油酸分子；碳链长度和烃基不饱和度几乎不影响脂肪酸中氧原子的态密度，其对脂肪酸性能的影响不是通过羧基作用的；脂肪酸与常见金属阳离子的相互作用能与其溶度积常数降低的规律一致，两者存在较好的对应关系；研究对了解脂肪酸捕收剂结构与性能的关系及开发新型脂肪酸类捕收剂有一定的理论意义和参考价值。
Abstract:This is an article in the field of mineral processing engineering. Fatty acid collectors are widely used in the flotation of oxidized ores, and the molecular structure is an important factor affecting the flotation performance. To reveal the effect of the structural change of fatty acid collector on its reaction activity from the microscopic point of view, the relationship between electronic structure and properties of fatty acid collectors was studied by the density functional theory. The research results show that the oxygen atom in oleic acid molecule and oleate ion has strong reaction activity, which is the bonding atom of oleic acid interaction with oxidized minerals. The two oxygen atoms of oleate ion have similar chemical activity, and the density of states at Fermi level is higher than that of oleic acid molecule, which makes the activity of oleate ion much stronger than that of oleic acid molecule. The length of the carbon chain and the unsaturation of the alkyl have almost no effect on the density of states of the oxygen atoms in fatty acids, their effect on the properties of fatty acids is not through the action of carboxyl groups. The interaction energy between fatty acids and common metal cations is consistent with the decrease of their solubility product constants, and there is a good corresponding relationship between them. The research has certain theoretical significance and reference value for understanding the relationship between the structure and performance of fatty acid collectors and developing new fatty acid collectors.
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表 1 油酸在不同泛函和基组下几何结构优化后的性质参数
Table 1. Properties of oleic acid in different functionals and basis sets under the geometric optimization
基组泛函 键长/Å 键角/° 能量/Ha C1-C2 C1-O1 C1-O2 O1-C1-O2 DNP 3.5 LDA PWC 1.485 1.259 1.256 115.924 -848.80 DNP 3.5 LDA VWN 1.485 1.259 1.256 115.924 -848.84 DNP 3.5 GGA PW91 1.504 1.268 1.267 116.049 -856.15 DNP 3.5 GGA BP 1.508 1.270 1.270 116.071 -856.39 DNP 3.5 GGA BPE 1.506 1.269 1.269 115.976 -855.37 DNP 3.5 GGA BLYP 1.516 1.274 1.274 116.223 -856.09 DNP 3.5 GGA BOP 1.520 1.275 1.275 116.148 -856.06 DNP+ 3.5 LDA PWC 1.484 1.259 1.255 115.841 -848.85 DNP+ 3.5 LDA VWN 1.484 1.259 1.255 115.851 -848.89 DNP+ 3.5 GGA PW91 1.505 1.268 1.267 115.914 -856.20 DNP+ 3.5 GGA BP 1.508 1.270 1.269 115.773 -856.34 DNP+ 3.5 GGA PBE 1.506 1.270 1.269 115.811 -855.42 DNP+ 3.5 GGA BLYP 1.515 1.274 1.273 116.191 -856.14 DNP+ 3.5 GGA BOP 1.520 1.275 1.275 116.047 -856.10 实验数据 1.50 1.27 1.27 119 
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表 2 常见脂肪酸捕收剂及其双键数量
Table 2. Common fatty acid collectors and the number of double bonds
脂肪酸 分子式 双键数 硬脂酸 C17H35COOH 0 棕榈油 C15H31COOH 0 肉豆蔻酸 C13H27COOH 0 月桂酸 C11H23COOH 0 油酸 CH3(CH2)7CH=CH(CH2)7COOH 1 亚油酸 CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH 2 亚麻酸 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH 3 桐酸 CH3(CH2)3CH=CHCH=CHCH=
CH(CH2)7COOH3
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表 3 饱和脂肪酸与Ca2+作用能与碳链长度的关系
Table 3. Relationship between interaction energy of saturated fatty acids with Ca2+ and carbon chain lengths
饱和脂肪酸 能量/Ha 与Ca2+作用能/
(kJ/mol)溶度积
Ksp（23 ℃）[25]正辛酸 -464.41 -621.82 2.7×10-7 癸酸 -543.05 -626.37 3.8×10-10 月桂酸 -621.69 -630.36 8.0×10-13 肉豆蔻酸 -699.11 -644.91 1.0×10-15 棕榈酸 -778.97 -649.25 1.6×10-16 硬脂酸 -857.61 -653.94 1.4×10-18
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表 4 油酸与常见金属阳离子的相互作用能与溶度积的关系
Table 4. Relationship between interaction energy and solubility product of oleic acid with common metal cations
金属阳离子 油酸/
(kJ/mol)能量/
(kJ/mol)相互作用能/
(kJ/mol)溶度积/
pKa [24]Mg2+ -856.388 -200.042 -419.751 13.8 Ba2+ -856.388 -7886.803 -496.144 14.9 Ca2+ -856.388 -677.519 -634.191 15.4 Zn2+ -856.388 -1779.366 -893.495 18.4 Cu2+ -856.388 -1640.487 -959.389 19.4
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