静态GM（0,6）灰色模型在预测气相色谱保留指数上的应用

本文从麦克雷诺（ＭｃＲｅｙｎｏｌｄｓ）相常数法出发推导了五种标准物质与任意溶质ｉ的色谱保留指数之间的关系符合灰色ＧＭ（０，６）模型，对它们进行了灰色建模。获得了很高的模型精度，并根据模型式预测了涂有不同固定液色谱柱中的溶质ｉ的保留指数。通过预测值与文献值的比较，得到了良好的预测精度。     

色谱灰色数模的建立及应用研究（Ⅳ）：CGM（1,1,N）模型的 …

应用灰色系统理论，推导出灰色Ｎ参数模型ＣＧＭ（１，１，Ｎ），突破了现有单参数灰色模型的局限性，并用该模型讨论了色谱保留值与分子结构参数间绎烷基苯的同分异构体色谱保留值及疏水性参数进行了预测，经实例验证，其预测精度较单参数灰色模型高，这为溶质保留行为的预测提供了一个实用方法，同时也拓宽了灰色模型的应用范围。     

色谱灰色数模的建立及其应用研究(Ⅰ)──连续GM(1,N)模型的建立及色谱保留行为的预测

应用灰色系统理论和最小二乘原理，推导出连续GM（1，N）模型，并将该模型用于高效液相色谱中溶质保留行为的预测．研究了烷烃、烷基苯及对羟基苯甲酸酯等化合物的容量因子与流动相组成、容量因子与碳数、保留时间与温度、保留时间与碳数的关系，并建立了相应的数学模型，经验证，预测结果良好．     

色谱灰色数模的建立及应用研究(Ⅳ)-CGM(1,1,N)模型的建立及烷基苯异构体保留行为的预测

应用灰色系统理论,推导出灰色N参数模型CGM(1,1,N),突破了现有单参数灰色模型的局限性.并用该模型讨论了色谱保留值与分子结构参数间的关系,对烷基苯的同分异构体色谱保留值及疏水性参数进行了预测.经实例验证,其预测精度较单参数灰色模型高,这为溶质保留行为的预测提供了一个实用方法,同时也拓宽了灰色模型的应用范围.     

灰色理论在液相色谱保留值研究中的应用

本文应用灰色理论中的ＧＭ（１，１）模型，对液相色谱中的Ф和ｋ＇的关系进行了研究，其结果达到用Ｓｃｈｏｅｎｍａｋｅｒｓ公式和卢佩章公式预测及计算ｋ＇的水平。结果指出：灰色理论完全适用于对色谱保留问题的研究，其方法也这无全能满足实际工作中的应用。     

微波消解法测定高锰酸盐指数

高锰酸盐指数是以高锰酸钾为氧化剂 ,测得化学需氧量 ,一般仅限于地表水、饮用水、生活污水的测定[1] 。常规的高锰酸盐指数测定法需在常压下用沸水浴加热 30ｍｉｎ(从水浴重新沸腾起计时 ) [2 ] ,所需时间较长。用微波消解法测定ＣＯＤｃｒ方法已有报道[3,4 ] ,但对高锰酸盐指数测定方法未见报道。本文采用微波消解的方法对高锰酸盐指数测定方法进行改进 ,在常压下 ,用理论ＣＯＤ 5 0 0ｍｇ·Ｌ-1的葡萄糖溶液作为分析试样。通过对火力调节、微波时间、酸度等条件试验 ,建立了微波消解测定高锰酸盐指数方法。结果表明 ,微波消解具有高效、…     

气相色谱灰色分析体系中未知组分保留指数的预测

提出在部分组分已知的气相色谱灰色体系中,利用已知组分的保留指数和保留时间推算死时间和正构烷烃的保留时间,再计算未知组分保留时间的方法,结果显示,在已知组分不是太少的情况下,该方法计算的死时间和正构烷烃的保留时间与实验值吻合,预测的保留指数也有较高的精度.     

连续型非等时空距灰色模型在液相色谱保留值研究中的应用

本运用灰色理论中的连续型等时空距ＧＭ（１，１）模型，对液相色谱中流动相组成与容量因子间的关系进行了研究，建立了可进行连续预测的数学模型，所建模型与实际情况吻合很好，经检验各模型精度均达到Ｉ级。     

水中高锰酸盐指数测量不确定度的评定

对GB 11892 - 1989《水质　高锰酸盐指数的测定》中酸性高锰酸钾氧化法测定水中高锰酸盐指数的测量不确定度进行了评定。通过对测量重复性、滴定管、移液管、标准溶液浓度等影响测量结果的不确定度分量的分析和量化 ,求得水中高锰酸盐指数测定结果的相对合成标准不确定度为 1.10× 10 -2 。     

基于二苯胺磺酸钠作指示剂的滴定法测定高锰酸盐指数

正高锰酸盐指数是地表水和地下水的常规监测指标,其国内标准早在1989年就已出台~([1]),并在环境、水利和疾控等部门开展多年。高锰酸盐指数是个条件性指标,对加热温度和加热时间的要求十分严格,且该指标在测定过程中受空白和反应温度等因素的制约,因此准确度不是很高。虽然国内学者对上述     

Determination of chemical oxygen demand in fresh waters using flow injection with on-line UV-photocatalytic oxidation and spectrophotometric detection

A flow injection manifold incorporating UV-photocatalytic oxidation for the determination of chemical oxygen demand (COD) in freshwater is reported. The method utilises the UV-photocatalytic oxidation of organic compounds instead of conventional heating (used in the standard method), with acidified potassium permanganate as the oxidant. Sodium oxalate, d-glucose and potassium hydrogen phthalate were used as COD standards. A 100 microL sample solution was injected into a 0.3 mol L(-1) H2SO4 carrier stream containing 0.1 mol L(-1) (NH4)2SO4, merged with a permanganate solution (8 x 10(-4) mol L(-1)) and passed through a 250 cm FEP (fluoroethylene polymer) photo-reaction coil wound around a 15 W UV lamp. The sample throughput was 30 h(-1), with an LOD (blank plus 3sigma) of 0.5 mg COD L(-1) and a linear range of 0.5-50 mg COD L(-1) (D-glucose, r2 = 0.9966). The method had good precision with relative standard deviations of 2.7% at 5 mg COD L(-1) and 1.2% at 20 mg COD L(-1) (n = 12) for glucose. Results for a COD certified reference material (QC Demand Quality Control Standard) were in good agreement with the certified COD value. Recovery from Tamar River water samples for all three COD standards was 83.0-111.0% and the COD values determined were in good agreement with those of a permanganate index reference method.     

关注长江水质——“绿行之踪”社会实践

2018年和2019年小学期,厦门大学本科生"绿行之踪"社会实践队赴重庆、上海等长江流域主要城市进行社会实践活动,采集了当地的水样,测定了水样中的磷酸根含量和高锰酸盐指数,同时进行了水资源保护的宣传活动和网络问卷调查。     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

Syntheses of 1‐(4‐methylsulfonylphenyl)‐5‐aryl‐1,2,3‐triazoles and ‐(4‐aminosulfonylphenyl)‐5‐aryl‐1,2,3‐triazoles

Condensation of 4‐methylsulfonylaniline with aryl aldehyde in ethanol‐tetrahydrofuran afforded the imino compound 3 . 1,3‐Cycloaddtion of diazomethane with compound 3 followed by oxidazation of the triazoline 4 with potassium permanganate gave 1‐(4‐methylsulfonylphenyl)‐5‐aryl‐1,2,3‐triazoles 5 . Similarly, condensation of 4‐(N,N‐dibenzylaminosulfonyl)aniline with aryl aldehyde followed by 1,3‐cycloaddition of diazomethane with the imino compound 11 and the subsequent oxidation of triazoline 12 with potassium permanganate yielded the triazole 13 . Debenzylation of compound 13 with sulfuric acid gave the desired compound 1‐(4‐aminosulfonylphenyl)5‐aryl‐1,2,3‐triazoles 14 .     

Triazolines 24. Permanganate-catalyzed low temperature thermolysis of 5-(4-pyridyl) substituted 1,2,3-triazolines

Potassium permanganate oxidation of 1-aryl-5-(4-pyridyl)-1,2,3-triazolines I in a benzene-water two-phase system using the phase-transfer catalyst tetrabutylammonium chloride yields the corresponding 1H-1,2,3-tri-azoles II . However, when the reaction is run in a single phase in anhydrous benzene alone, the products are not triazoles, but imines III that can normally be obtained only by high-temperature thermolysis of the tri-azolines. The presence of both potassium permanganate and tetrabutylammonium chloride to yield the benzene soluble tetrabutylammonium permanganate ion pair appears essential for imine formation, although only in catalytic amounts. Thus a reaction pathway is proposed, which involves the initial coordination of the pyridyl nitrogen with the manganese atom of the permanganate ion leading to IV , followed by loss of nitrogen and regeneration of the permanganate ion via the dihydropyridine intermediates, V and VI , to yield the enamine VII , which tautomerizes to the imine III . Supportive evidence for the formation of IV is derived from the failure of 1,5-diaryl- and l-aryl-5-(3-pyridyl)triazolines to yield the respective imines; they lack the structural requirements necessary to comply with the proposed mechanism, and are recovered unchanged. Unlike the high temperature pyrolysis, the permanganate catalyzed low temperature thermolysis reactions provide cleaner products in better yields. Thus, the low temperature thermolysis may afford a route for the synthesis of clean samples of l-arylimino-l-ethyl-4-pyridines, especially when the triazolines are on hand.     

Synthesis of Several 2-Azafluorenones and 5H[1]Benzopyrano[3,4-c]Py Riding-Ones

Convenient syntheses of 2-azafluorenones 5a-f and 5H[1]benzopyrano[3,4-c]pyridin-5-ones 6a-b were performed by using intramolecular cyclization of 4-arylnicotinic acids 4a-F. 4a-f were obtained via permanganate oxidation from the corresponding of 4-arylpyridines 3a-f in good yields.     

Amination of 4-nitropyridazine 1-oxides by liquid ammonia/potassium permanganate

Treatment of 4-nitropyridazine 1-oxide ( 1a ) 3-methoxy-6-chloro-4-nitropyridazine 1-oxide ( 1b ) or 3,6-dimethoxy-4-nitropyridazine 1-oxide ( 1c ) with a solution of potassium permanganate in liquid ammonia gives in reasonable-to-good yields the corresponding 5-amino-4-nitropyridazine 1-oxides (75%, 54% and 62%, respectively). 3,6-Dimethoxypyridazine ( 4a ) and 3-methoxypyridazine ( 4b ) are converted into the corresponding 4-aminopyridazines 6a,6b on treatment with potassium amide/liquid ammonia/potassium permanganate (yield 50 and 22% respectively). In the last-mentioned reaction besides 6b 3,3′-dimethoxy 4,4′-bipyridazine (7, 23%) was obtained. It is suggested that the neutral 1:1 σ-adducts formed between ( 1a–1c ) and liquid ammonia and the anionic σ-adducts, formed between ( 5a–5b ) and potassium amide are intermediates in this amino-oxidation reaction.     

Evidence of competitive mechanisms during oxidation of CS(2)N(-)(3) by permanganate ion in alkaline solution

The oxidation of the 1,2,3,4-thiatriazole-5-thiolate ion, CS(2)N(-)(3), by permanganate ions in alkaline medium has been investigated over a wide range of oxidant concentrations. With a moderate excess of permanganate ion a 17-electron reaction takes place, yielding sulphate, nitrogen and carbon dioxide. With a high permanganate concentration the pseudohalide undergoes a 26-electron reaction yielding sulphate, carbon dioxide and nitrite as final products. These two different stoichiometries arise from the existence of competitive mechanisms and the ratio C(MnO(-)(4))/C(CS(2)N(-)(3)) will determine the course of the reaction.     

Spectrophotometric determination of micro amounts of tetrathionate via its oxidation with permanganate

The reaction conditions of tetrathionate with permanganate were investigated by varying reaction time, temperature and amounts of sulphuric acid and permanganate. Under the optimal conditions for the reaction of tetrathionate with permanganate, both penta- and hexathionate were also oxidised; each one mol of polythionates (S _x O ₆ ^2– x=4, 5 and 6) reacts with (x–1.5) mol of permanganate. The proposed method is based on the reaction of tetrathionate with a given excess amount of permanganate in a sulphuric acid medium and on the spectrophotometric measurement of the iodine as triiodide formed by the oxidation of iodide with the excess of permanganate. This method could be successfully applied to the determinations of tetrathionate (4 × 10^–7 to 2 × 10^–5 M), pentathionate (3 × 10^–7 to 1.43 × 10^–5 M) and hexathionate (2 × 10^–7 to 1.11 × 10^–5 M), and gave a higher sensitivity than any previous methods without solvent extraction.     

Oxidation of perfluoro-substituted derivatives of 1,3-diazines and 1,2,4-triazoles

Oxidation of 6-perfluoro-substituted 2-amino-4-methylpyrimidines and 5-amino-3-perfluoro(1,4-dimethyl-2,5-dioxaoctyl)-1,2,4-triazole with potassium permanganate and of 3-perfluoro-substituted 5-mercapto-and 5-amino-1,2,4-triazoles with hydrogen peroxide in alkaline solution was studied.