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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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

Received: 2025-04-19 Accepted: 2025-09-03

ZTFLH:

O657.32

Corresponding Authors: DUAN Ning E-mail: ningduan@tongji.edu.cn

Cite this article:

XU Yan-li,XU Fu-yuan,DUAN Ning. UV-Visible Spectral Characteristics and Quantitative Analysis of the MnSO₄-H₂SO₄ System[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(11): 3160-3168.

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https://www.gpxygpfx.com/EN/10.3964/j.issn.1000-0593(2025)11-3160-09 OR https://www.gpxygpfx.com/EN/Y2025/V45/I11/3160

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