The Relationship between Mineral Structure and Floatability Discussed from the Principle of Coordination Field
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摘要:
从配位场原理角度研究了矿物晶体结构与可浮选性的关系，解释了晶体结构对矿物可浮性的影响。赤铁矿和黄铁矿中的铁离子分别具有d5和d6构型，且分别拥有0对和3对π电子，致使黄药捕收剂无法与赤铁矿形成反馈π键，而可以与黄铁矿形成较强的反馈π键，因而黄药对黄铁矿有较强的捕收作用而对赤铁矿无捕收作用。姜泰勒效应解释了黄药捕收剂对氧化铜和硫化铜矿物的捕收差异，即氧化铜中占据在dz2轨道上的电子会排斥黄药，因而不利于Cu2+离子与黄药类捕收剂的作用。对于含有d10锌离子的闪锌矿，d轨道活性较大的金属离子如铜、金、银离子都有较大的极化率，能增强了离子和捕收剂分子的共价作用，因而对闪锌矿具有活化作用。在具有单S配位的磁黄铁矿晶体中，磁黄铁矿Fe2+只有1对π电子，与黄药捕收剂的反馈π键作用弱，并且没有空的d轨道，不利于与黄药形成作用较强的内轨型配位，造成黄药对磁黄铁矿的捕收作用弱于黄铁矿。对于含有四配位Fe2+离子的含铁闪锌矿，铁离子的π电子对为1对，与黄药的反馈π键作用弱，因而含铁闪锌矿的可浮性与黄铁矿不同。黄铜矿中铜的3d π电子对多于铁，因而铜与黄药类捕收剂的共价配位作用更强，使铜成为反应活性中心，此外铁离子的自旋耦合效应增强了铜离子的活性。
Abstract:This study investigated the relationship between mineral crystal structure and floatability from the perspective of ligand field theory, explaining the influence of crystal structure on mineral floatability. The iron ions in hematite and pyrite possess d5 and d6 electronic configurations respectively, with 0 and 3 pairs of π electrons correspondingly. This difference prevents xanthate collectors from forming feedback π−bonds with hematite while enabling strong feedback π−bond formation with pyrite, resulting in strong collecting power of xanthate for pyrite but none for hematite. The Jahn−Teller effect explains the differential collecting behavior of xanthate towards copper oxide and copper sulfide minerals. In oxidized copper minerals, electrons occupying the dz2 orbital repel xanthate molecules, thereby hindering the interaction between Cu2+ ions and xanthate-type collectors. For sphalerite containing d10 zinc ions, ions such as copper, gold, and silver exhibit high polarizability, which enhances the covalent interaction between these ions and collector molecules, thereby activating sphalerite. In pyrrhotite crystals with single S coordination, Fe2+ possesses only one pair of π electrons, leading to weak π back−bonding interaction with xanthate. The absence of vacant d−orbitals further hinders the formation of strong inner−sphere coordination complexes, making pyrrhotite less floatable than pyrite. For iron−bearing sphalerite containing tetrahedrally coordinated Fe2+ ions, the single π−electron pair results in weak π back−bonding with xanthate, creating distinct floatability characteristics compared to pyrite. In chalcopyrite, copper possesses more 3d π electron pairs than iron, leading to stronger covalent coordination with xanthate-type collectors, establishing copper as the reactive site. Additionally, spin−coupling effects of iron ions enhance the activity of copper ions.
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表 1 不同配位结构下的σ和π轨道[7]
Table 1. The σ and π orbitals under different coordination structures
配位数 结构 σ轨道 π轨道 备注 2 直线 s px py pz dxz dyz 沿x轴成键 3 平面等边
三角形s px py dxy pz dxz dyz xy平面成键 4 平面
正方形
dxz dyz xy平面成键 正四面体 dxy dzz dyz dxy dxz dyz 
5 三角双锥 
dxz dyz 
dxy四方锥 
dxy dxz dyz 6 正八面体 
dxy dxz dyz 8 立方体 dxy dxz dyz dxy dxz dzy 
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