碳链结构对黄药捕收剂分子量子化学性质的影响

刘岱昕; 陈远林; 丁鸣援; 李玉琼

doi:10.13779/j.cnki.issn1001-0076.2025.08.001

碳链结构对黄药捕收剂分子量子化学性质的影响

1.
广西大学资源环境与材料学院，广西南宁 530004

2.
广西高校矿物工程重点实验室，广西南宁 530004

基金项目: 广西科技重大专项（桂科AA23073018）；广西自然科学基金（2025GXNSFAA069648）

详细信息

作者简介: 刘岱昕（1998—），男，山西长治人，硕士研究生，主要从事矿物浮选研究工作，E-mail：1102114353@qq.com

通讯作者: 李玉琼（1982—），女，广西桂林人，博士，教授，博士生导师，主要从事矿物浮选研究工作，E-mail：yql@gxu.edu.cn。

中图分类号: TD91

收稿日期: 2024-12-26

刊出日期: 2025-04-15

Effect of Carbon Chain Structure on the Quantum Chemical Properties of Xanthate Collector Molecules

1.
School of Resources, Environment and Materials, Guangxi University, Nanning 530004, Guangxi, China

2.
Guangxi Higher School Key Laboratory of Minerals Engineering, Nanning 530004, Guangxi, China

More Information

Corresponding author: LI Yuqiong, yql@gxu.edu.cn

Received Date: 26 December 2024

Publish Date: 15 April 2025

摘要

摘要:
黄药是硫化矿浮选常用的捕收剂，其碳链长度和结构影响其捕收性能。基于密度泛函理论（DFT）计算了C₁～C₅碳链长度的正构和异构黄药的极性官能团−OCSS⁻的键结构特征、前线轨道能量，并计算了S原子的轨道系数、Mulliken电荷和亲电亲核性。结果表明，碳链长度对捕收剂官能团键结构特征影响并不显著，碳链上的H原子与极性基S原子会发生较弱的氢键作用，且随着碳链的增长而增强，造成了官能团键结构的细微差异。黄原酸根离子极性官能团中的两个S原子电荷相近，均是亲核的，但S原子的亲核性存在差异，导致在矿物表面具有不同的吸附能力。除丁基和异丁基黄原酸根离子外，异构体黄原酸根离子的最高占据分子轨道（HOMO）与黄铁矿的最低空轨道（LUMO）的能量差，低于正构体黄原酸根离子的能量差，这说明异构体有利于增强捕收剂的捕收能力，这与Fe²⁺离子和黄原酸根离子的结合能计算结果一致，其中，异丙基和异丁基黄原酸根离子与Fe²⁺离子的结合能较大。
- 黄原酸根离子 /
- 密度泛函理论 /
- 前线轨道 /
- 反应活性
Abstract:
Xanthates are commonly used as flotation collectors for sulfide ores, and the length and structure of the carbon chain will affect their capture performance. Based on density functional theory (DFT), the bond structure characteristics and frontier orbital energies of polar functional groups −OCSS⁻ of normal and isomeric xanthate ions with C₁ to C₅ carbon chain lengths were calculated, the orbital coefficient, Mulliken charge, electrophilicity and nucleophilicity of the S atoms were also calculated. The results show that the length of the carbon chain has no significant effect on the structural characteristics of the functional group bonds of the collector, the H atoms on the carbon chain have weak hydrogen bonding with the polar group S atoms, which increase with the growth of the carbon chain, resulting in subtle differences in the functional group bond structure. The two S atoms in the polar functional groups of xanthate ions have similar charges and are both nucleophilic, but the nucleophilicity of the S atoms varies, resulting in different adsorption abilities on mineral surfaces. Except for butyl and isobutyl xanthate ions, the energy difference between the highest occupied molecular orbital (HOMO) of isomeric xanthate ions and the lowest unoccupied orbital (LUMO) of pyrite is lower than that of the normal xanthate ions. This indicates that isomers are beneficial for enhancing the collection ability of collectors, which is consistent with the calculated binding energy of xanthate ions and Fe²⁺. Among them, isopropyl and isobutyl xanthate ions have higher binding energies with Fe²⁺.
- xanthate ions /
- density functional theory /
- frontier orbital /
- reactivity

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图 1 乙基黄原酸根离子结构

Figure 1.

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图 2 捕收剂前线分子轨道构型

Figure 2.

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图 3 药剂离子与铁离子作用模型

Figure 3.

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表 1 乙黄药官能团（−OCSS⁻）在不同泛函和基组下几何结构优化后的结构参数

Table 1. Structures of ethyl xanthate in different functionals and basis sets after the geometric optimization

基组	泛函	键长/Å（1 Å= 0.1 nm）			键角 (∠S1−C−S2)/(°)
基组	泛函	R(C−O)	R(C−S1)	R(C=S2)	键角 (∠S1−C−S2)/(°)
DNP3.5	LDA VWN	1.380	1.672	1.687	126.7
	LDA PWC	1.382	1.673	1.687	126.7
	GGA PW91	1.385	1.725	1.705	125.2
	GGA PBE	1.380	1.726	1.703	126.4
	GGA BLYP	1.377	1.727	1.722	126.8
	GGA RPBE	1.383	1.725	1.713	125.7
	B3LYP	1.386	1.724	1.710	127.3
DND3.5	LDA VWN	1.378	1.671	1.686	126.6
	LDA PWC	1.378	1.669	1.686	126.6
	GGA PW91	1.381	1.667	1.703	126.6
	GGA PBE	1.383	1.723	1.702	126.2
	GGA BLYP	1.377	1.725	1.721	127.2
	GGA RPBE	1.385	1.724	1.713	125.5
	B3LYP	1.322	1.727	1.710	127.3
DNP+	LDA VWN	1.321	1.666	1.680	125.9
	LDA PWC	1.321	1.668	1.681	125.9
	GGA PW91	1.377	1.668	1.697	125.9
	GGA PBE	1.377	1.670	1.704	125.9
	GGA BLYP	1.378	1.724	1.714	126.2
	GGA RPBE	1.381	1.725	1.705	125.1
实验值		1.350	1.700	1.670	124.0

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表 2 黄原酸根离子结构

Table 2. Ionic structure of xanthate collectors

结构式	名称	疏水基
	甲基黄药	−CH₃
	乙基黄药	−C₂H₅
	丙基黄药	−C₃H₇
	异丙基黄药	−C₃H₇
	丁基黄药	−C₄H₉
	异丁基黄药	−C₄H₉
	戊基黄药	−C₅H₁₁
	异戊基黄药	−C₅H₁₁

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表 3 捕收剂离子官能团的键长和键角

Table 3. Bond length and bond angle of functional group of the collectors

疏水基	名称	键长/Å			键角
疏水基	名称	R(C−O)	R(C−S1)	R(C=S2)	(∠S1−C−S2)/(°)
−CH₃	甲基黄药	1.394	1.717	1.713	127.0
−C₂H₅	乙基黄药	1.377	1.727	1.722	126.8
−C₃H₇	丙基黄药	1.393	1.719	1.716	126.1
−C₃H₇	异丙基黄药	1.402	1.718	1.710	125.4
−C₄H₉	丁基黄药	1.395	1.727	1.710	125.8
−C₄H₉	异丁基黄药	1.395	1.723	1.712	126.1
−C₅H₁₁	戊基黄药	1.390	1.720	1.718	126.5
−C₅H₁₁	异戊基黄药	1.394	1.718	1.715	126.4

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表 4 黄原酸根离子中的S1原子与碳链上H原子之间的距离

Table 4. The distance between the S atom and the hydrogen in the carbon chain of different xanthate ions

疏水基	名称	距离/Å
疏水基	名称	D(S1−H1)	D(S1−H2)
−CH₃	甲基黄药	2.541	3.504
−C₂H₅	乙基黄药	2.927	3.061
−C₃H₇	丙基黄药	2.896	3.375
−C₃H₇	异丙基黄药	3.345	——
−C₄H₉	丁基黄药	2.880	3.301
−C₄H₉	异丁基黄药	2.848	3.351
−C₅H₁₁	戊基黄药	2.827	3.253
−C₅H₁₁	异戊基黄药	2.789	3.246

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表 5 捕收剂与黄铁矿前线轨道能量

Table 5. Collector with pyrite frontier orbital energy

疏水基	名称	前线轨道能量/eV		E₁=\|E_HOMO−X−E_{LUMO−pyrite}\|	E₂=\|E_{HOMO− pyrite} −E_LUMO−X\|
疏水基	名称	HOMO	LUMO	E₁=\|E_HOMO−X−E_{LUMO−pyrite}\|	E₂=\|E_{HOMO− pyrite} −E_LUMO−X\|
−CH₃	甲基黄药	−3.991	−1.398	0.171	3.815
−C₂H₅	乙基黄药	−3.953	−1.191	0.134	4.022
−C₃H₇	丙基黄药	−3.955	−1.338	0.136	3.875
−C₃H₇	异丙基黄药	−3.853	−1.595	0.034	3.618
−C₄H₉	丁基黄药	−3.957	−1.293	0.138	3.920
−C₄H₉	异丁基黄药	−3.962	−1.367	0.143	3.846
−C₅H₁₁	戊基黄药	−3.974	−1.319	0.155	3.894
	异戊基黄药	−3.968	−1.386	0.149	3.827
	黄铁矿	−5.213	−3.819

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表 6 官能团中原子的前线轨道系数

Table 6. Frontier orbital coefficients of atoms in functional groups

疏水基	名称	HOMO				LUMO
疏水基	名称	S1 3p	S2 3p	C 2p	O 2p	S1 3p	S2 3p	C 2p	O 2p
−CH₃	甲基黄药	0.573	0.632	0.023	0.133	0.558	0.559	0.854	0.324
−C₂H₅	乙基黄药	0.524	0.708	0.025	0.102	0.550	0.523	0.863	0.405
−C₃H₇	丙基黄药	0.509	0.683	0.025	0.129	0.556	0.538	0.854	0.341
−C₃H₇	异丙基黄药	0.677	0.533	0.019	0.253	0.520	0.521	0.752	0.209
−C₄H₉	丁基黄药	0.630	0.563	0.021	0.084	0.497	0.537	0.817	0.392
−C₄H₉	异丁基黄药	0.556	0.641	0.020	0.082	0.440	0.419	0.684	0.327
−C₅H₁₁	戊基黄药	0.535	0.656	0.034	0.121	0.547	0.541	0.853	0.358
−C₅H₁₁	异戊基黄药	0.508	0.668	0.038	0.132	0.545	0.554	0.839	0.324

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表 7 S原子的Mulliken电荷值

Table 7. Mulliken charge value of the S atom

疏水基	名称	S1/e	S2/e
−CH₃	甲基黄药	−0.663	−0.674
−C₂H₅	乙基黄药	−0.681	−0.701
−C₃H₇	丙基黄药	−0.671	−0.683
−C₃H₇	异丙基黄药	−0.663	−0.649
−C₄H₉	丁基黄药	−0.691	−0.667
−C₄H₉	异丁基黄药	−0.667	−0.683
−C₅H₁₁	戊基黄药	−0.673	−0.686
−C₅H₁₁	异戊基黄药	−0.668	−0.678

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表 8 S原子的亲电亲核指数

Table 8. Electrophilic and nucleophilic index of S atom

疏水基	名称	亲电攻击指数f ⁻		亲核攻击指数f ⁺		f ²（r）
疏水基	名称	S1	S2	S1	S2	S1	S2
−CH₃	甲基黄药	0.420	0.469	0.359	0.371	−0.061	−0.098
−C₂H₅	乙基黄药	0.418	0.477	0.358	0.362	−0.060	−0.115
−C₃H₇	丙基黄药	0.418	0.474	0.359	0.367	−0.059	−0.107
−C₃H₇	异丙基黄药	0.435	0.447	0.375	0.374	−0.060	−0.073
−C₄H₉	丁基黄药	0.483	0.409	0.363	0.360	−0.120	−0.049
−C₄H₉	异丁基黄药	0.412	0.479	0.361	0.368	−0.051	−0.111
−C₅H₁₁	戊基黄药	0.422	0.468	0.358	0.366	−0.064	−0.102
−C₅H₁₁	异戊基黄药	0.421	0.468	0.358	0.370	−0.063	−0.098

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表 9 药剂与2价铁离子作用结果

Table 9. Result of the interaction of the reagent with iron ions

疏水基	名称	键长/Å		结合能/（kJ·mol⁻¹）
疏水基	名称	Fe−S1	Fe−S2	结合能/（kJ·mol⁻¹）
−CH₃	甲基黄药	2.311	2.296	−306.088
−C₂H₅	乙基黄药	2.286	2.280	−309.522
−C₃H₇	丙基黄药	2.290	2.282	−311.101
−C₃H₇	异丙基黄药	2.301	2.300	−311.944
−C₄H₉	丁基黄药	2.292	2.288	−311.216
−C₄H₉	异丁基黄药	2.299	2.294	−312.000
−C₅H₁₁	戊基黄药	2.289	2.284	−311.502
−C₅H₁₁	异戊基黄药	2.315	2.308	−311.303

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