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基于KMnO/KSO/亚硫酸氢钠品红反应体系温度效应直接自动测定红葡萄酒中的甲醇含量

Direct automatic determination of the methanol content in red wines based on the temperature effect of the KMnO/KSO/fuchsin sodium sulfite reaction system.

作者信息

Li Yong-Sheng, Mo La-Mei, Gao Xiu-Feng

机构信息

School of Chemical Engineering, Sichuan University Chengdu 6100651 China

West China School of Basic Medical Sciences & Forensic Medicine, Sichuan University Chengdu 610065 China

出版信息

RSC Adv. 2018 Feb 23;8(15):8426-8434. doi: 10.1039/c8ra00307f. eCollection 2018 Feb 19.

Abstract

The standard method for methanol assay in wine is based on a methanol/KMnO/HCO/fuchsin sodium sulfite (FSS) reaction system. However, it is difficult to control the degree of colour and the temperature of the reaction product in this assay, and its repeatability is also poor due to the generation of CO and CO in the reaction. Therefore, to solve these problems, potassium metabisulfite was selected to replace HCO, and an automatic analysis method was developed which can realize rapid and accurate determination of methanol and can be used to make an online analyzer. It was discovered that the reactions of methanol/KMnO and acetaldehyde/FSS are exothermic, while the reactions of methanol/KMnO and formaldehyde/FSS are endothermic. Consequently, based on the temperature effect, not only was the interference of ethanol eliminated in detecting methanol in wines, the purpose of the research was achieved to directly and accurately determine methanol without sample pretreatment. By optimizing the system, the obtained conditions for determining methanol in wines were as follows: 20 g L concentration for KMnO; 3 g L concentration for FSS; 40 cm length for the first reaction coil (RC); 100 cm length for RC; 700 cm (I.D.: 0.8 mm) length for RC; 50 °C for RC; about 20 °C for RC and RC; 330 μL for the sample volume. The method showed a linear response in the range 25-1000 mg L, with a 0.6% RSD, 8.8 mg L detection limit and 25 samples per h, and was successfully used for testing representative wine samples. It also obtained better accuracy than previous methods. Due to its superiority in automated operation, reproducibility, analysis speed and test cost, this method and system can serve as a supplementary standard for methanol assay, and for the quality control of the winemaking process and the final wine-product, as well as for low-alcohol drinks.

摘要

葡萄酒中甲醇含量测定的标准方法是基于甲醇/高锰酸钾/碳酸氢盐/品红亚硫酸钠(FSS)反应体系。然而,该测定方法难以控制反应产物的颜色深浅和温度,并且由于反应中会生成一氧化碳和二氧化碳,其重复性也较差。因此,为了解决这些问题,选用焦亚硫酸钾替代碳酸氢盐,并开发了一种自动分析方法,该方法能够实现甲醇的快速准确测定,可用于制作在线分析仪。研究发现,甲醇/高锰酸钾与乙醛/FSS的反应是放热反应,而甲醇/高锰酸钾与甲醛/FSS的反应是吸热反应。因此,基于温度效应,不仅在葡萄酒中甲醇检测时消除了乙醇的干扰,还实现了无需样品预处理即可直接准确测定甲醇的研究目的。通过优化该系统,得到葡萄酒中甲醇测定的条件如下:高锰酸钾浓度为20 g/L;FSS浓度为3 g/L;第一反应盘管(RC)长度为40 cm;RC长度为100 cm;RC长度为700 cm(内径:0.8 mm);RC温度为50 °C;RC和RC温度约为20 °C;进样量为330 μL。该方法在25 - 1000 mg/L范围内呈线性响应,相对标准偏差为0.6%,检测限为8.8 mg/L,每小时可检测25个样品,并成功用于检测代表性葡萄酒样品。其准确性也优于以往方法。由于该方法和系统在自动化操作、重现性、分析速度和检测成本方面具有优势,可作为甲醇含量测定的补充标准,用于葡萄酒酿造过程及最终葡萄酒产品以及低酒精饮料的质量控制。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c9c6/9078531/1d0e398ec388/c8ra00307f-f1.jpg

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