MnSO4-H2SO4体系紫外可见光谱特性及定量分析

doi:10.3964/j.issn.1000-0593(2025)11-3160-09

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摘要：湿法冶金工业中高酸高锰体系（H₂SO₄≤2 mol·L^-1, Mn²⁺≤1.2 mol·L^-1）的监测面临传统方法预处理复杂、响应慢的瓶颈。在高浓度H₂SO₄体系中对Mn²⁺浓度的监测对于湿法冶金工艺的过程控制和优化至关重要。旨在开发一种基于紫外可见（UV-Vis）光谱的快速直测方法，解决Mn²⁺与H₂SO₄光谱重叠的干扰问题，能够直接测定MnSO₄-H₂SO₄体系中的Mn²⁺浓度，为工业高频次监测提供创新解决方案。为此系统测定了0～18 mol·L^-1 H₂SO₄溶液的光谱特性，结合光谱相似性分析[包括光谱相关性度量（SCM）、欧几里得距离度量（EDM）和光谱信息散度（SID）]，筛选抗干扰波长；通过长光程增强策略（100 mm）提升Mn²⁺检测灵敏度；建立工业浓度范围（Mn²⁺≤60 g·L^-1）内的定量模型。结果表明：H₂SO₄在180～230 nm 的吸收峰（λ_max=185～195 nm）与MnSO₄信号严重重叠，其浓度依赖性位移及Mn²⁺配位增强SO^2-₄吸光是核心干扰源；400 nm波长处H₂SO₄无吸收且Mn²⁺特征稳定，模型预测绝对相对误差（absolute relative error, |RE|）与相对标准偏差（RSD）均<5%，R²>0.99。首创“光谱干扰解耦-长光程增强”协同策略，开发了一种无需稀释或预处理的UV-Vis光谱检测方法，实现在高浓度H₂SO₄溶液中对Mn²⁺的快速、精准监测。该方法具备快速、低成本和高精度，适用于工业浸出和电解精炼的监测需求，同时对其他无机盐电解体系的分析具有指导意义，为提升湿法冶金效率、降低环境负荷提供了重要参考。

关键词：MnSO₄-H₂SO₄电解液；紫外可见光谱；高浓度Mn²⁺直测；光谱相似性分析

Abstract：The complex pretreatment requirements and delayed analytical response inherent in conventional methods constitute major challenges for monitoring high-acid, high-manganese systems (H₂SO₄≤2 mol·L^-1, Mn²⁺≤1.2 mol·L^-1) within the hydrometallurgical industry. For effective process management and optimization, rapid and accurate monitoring of Mn²⁺ concentration within high-concentration H₂SO₄ matrices is crucial. This study aimed to develop a rapid and direct determination method based on ultraviolet-visible (UV-Vis) spectroscopy to overcome spectral interference arising from the significant overlap between the absorbances of Mn²⁺ and H₂SO₄. The goal was to enable direct quantification of Mn²⁺ within MnSO₄-H₂SO₄ systems, thereby providing an innovative solution for high-frequency industrial monitoring. The study systematically characterized the spectral properties of H₂SO₄ solutions across a concentration range of 0～18 mol·L^-1. Utilizing spectral similarity analysis techniques—including Spectral Correlation Measure (SCM), Euclidean Distance Measure (EDM), and Spectral Information Divergence(SID)—wavelengths exhibiting minimal H₂SO₄ interference were identified. Furthermore, the detection sensitivity for Mn²⁺ was enhanced using a long optical path strategy (100 mm). A robust quantitative model was established for Mn²⁺ within the industrially relevant concentration range (≤60 g·L^-1). Key findings demonstrate that the absorption peak of H₂SO₄ within the 180～230 nm region (λ_max≈185～195 nm) shows substantial overlap with the MnSO₄ absorption. The core sources of interference identified were the concentration-dependent wavelength shift of this H₂SO₄ peak and the enhanced SO^2-₄ absorption due to Mn²⁺ coordination. Crucially, H₂SO₄ exhibits negligible absorption at 400 nm, a wavelength where the Mn²⁺ complex showed stability. Model validation yielded excellent performance: predicted absolute relative errors |RE| and relative standard deviations (RSD) both remained below 5%, with a coefficient of determination (R²) exceeding 0.99. This research pioneered a collaborative spectral interference decoupling-long optical path enhancement strategy. A UV-Vis spectroscopic detection method was developed that achieves rapid and accurate quantification of Mn²⁺ in high-concentration H₂SO₄ solutions, eliminating the need for dilution or pretreatment. This approach offers advantages in speed, cost-effectiveness, and precision, making it well-suited for monitoring requirements in industrial leaching and electrolytic refining processes. The strategy holds significant guiding potential for analyzing other inorganic salt electrolysis systems and provides a crucial foundation for improving hydrometallurgical efficiency while reducing environmental burdens.

Key words：MnSO₄-H₂SO₄ electrolyte; UV-visible spectroscopy; Direct determination of high-concentration Mn²⁺; Spectral similarity analysis

收稿日期: 2025-04-19 修订日期: 2025-09-03

中图分类号:

O657.32

基金资助: 国家自然科学基金项目（52174385），国家重点研发计划项目（2023YFC3904000）资助

通讯作者: 段宁 E-mail: ningduan@tongji.edu.cn

作者简介: 徐艳丽，女，1993年生，同济大学环境科学与工程学院博士研究生 e-mail: 2011699@tongji.edu.cn

引用本文:

徐艳丽，徐夫元，段宁. MnSO₄-H₂SO₄体系紫外可见光谱特性及定量分析[J]. 光谱学与光谱分析, 2025, 45(11): 3160-3168.
XU Yan-li, XU Fu-yuan, DUAN Ning. UV-Visible Spectral Characteristics and Quantitative Analysis of the MnSO₄-H₂SO₄ System. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(11): 3160-3168.

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