用DSPCF光度法测定NO_2~-和NO_3~-

文献报道,DSPCF溶于稀盐酸中为红色,当有NO_2~-存在时,可使DSPCF的四氮基转化为无色氧化型,并可破坏除铌以外的其它元素与DSPCF形成的配合物。当加入DSPCF的量一定时,NO_2~-含量逐渐增加,在酸性条件下,佛水浴中加热4—5分钟,红色逐渐减褪。我们利用此褪色反应,探讨了测定NO_2~-的最佳条件,提出了测定NO_2~-的新方法,其摩尔吸光系数ε_(470)=5.8×10~4。若用还原剂将NO_3~-还原为NO_2~-,亦可测定NO_3~-。本法可用来测定饮用水和污水中NO_2~-和NO_3~-。 (一)试剂和仪器     

鉴别NO_3~-和NO_2~-的两种方法

在中学化学中鉴定NO_3~-最常用的方法是用FeSO_4溶液使之产生棕色的物质(FeSO_4·NO),而鉴定NO_2~-也常用上述方法。那么如何区别这两种离子呢? 鉴别NO_3~-和NO_2~-两种离子时,我们可以用一种试剂就可以把它们区分开。目前方法很多,现在介绍两种方法,一种是以FeSO_4     

离子色谱中高质量浓度的Cl~-对痕量NO_2~-,Br~-和NO_3~-测定的影响

在 3支不同性质的离子色谱柱上 ,研究了高质量浓度的Cl- 对痕量NO2 - ,Br- 和NO3- 分离分析的影响 ,提出在分离过程中同时存在自身洗脱效应和在柱流动相变化两种洗脱机理。当Cl- 与待测离子色谱峰重叠时 ,在抑制器处置换出的H 使弱酸型阴离子分子化 ,给定量测定带来偏差 ,而对于强酸型阴离子则没有影响。由实验得到用峰高法测定NO-2 ,Br- 和NO3- 等 3种阴离子时在不同Cl- 质量浓度下的线性范围以及能够准确定量的Cl- 的最大质量浓度。     

抑制型离子色谱法测定白酒中的F~-、CI~-、NO_2~-、H_2PO_4~-、NO_3~-

用抑制型离子色谱法测定白酒中的F~-、cl~-、NO_2~-、H_2PO_4~-、NO_3~-。流动相为4mmoL/L Na_2CO_3-3mmoL/L NaHCO_3混合溶液,流速为1.5mL/min,进样量为0.5mL,在最佳色谱条件下,5种无机阴离子10min内实现基线分离。F~-、cl~-、NO_2~-、H_2PO_4~-、NO_3~-的检出限分别为0.008、0.012、0.030、0.068、0.077mg/L。测定结果的相对标准偏差分别为1.86％、1.30％、2.06％、1.82％、1.50％,回收率分别为108.0％、94.0％、101.0％、98.7％、94.4％。     

多波长线性回归——阶导数分光光度法同时测定水中 NO_3~-和 NO_2~-

NO_3~-和 NO_2~-是水质监测的重要指标,测定方法已有报道,但多数采用常规分光光度法,操作较为麻烦,灵敏度不高。本文提出了多波长线性回归一阶导数分光光度法同时测定两个组分的原理,并应用于水中 NO_3~-和 NO_2~-的同时测定。样品分析结果表明,精密度和准确度良好,并且,本法的吸光系数较常规多波长线性回归法的吸光系数提高10倍,最低检测限(本法是0.004μg/ml)较常规多波长线性回归法的最低检测限降低了10倍。该法具有简单、灵敏、准确的优点。     

杜利特尔分析与多元校正法应用于紫外分光光度法同时测定NO_3~-和NO_2~-

杜利特尔法是一种数值分析方法,它通过对矩阵进行三角分解,从而简化运算,提高准确度。将杜利特尔法与多元校正相结合,用于紫外光谱重叠比较严重的NO3-和NO2-两组分体系谱图,测定的相对误差在-4.56%~9.02%范围,明显好于P矩阵计算结果(-21.03%~36.40%),表明杜利特尔多元校正法在解析多组分重叠谱图方面具有一定的优越性。     

应用2,6-二甲基苯酚测定NO_3~-的方法研究

由于硝酸盐的可溶性,因此它在水体中的存在是非常广泛的。在饮水卫生和环境保护中它的测定也是重要的项目之一。本文研究了用2,6-二甲基苯酚作NO_3~-的测定试剂,用硫酸汞试剂消除Cl~-的干扰,可容许水样中Cl~-的存在达600ppm。用正交试验法研究了最佳的测定条件,在0.45～3,800ppm NO_3~-的浓度范围内,6个样品的平均回收率为95.37％,平均相对偏差为4.12％。方法在310毫微米波长下作NO_3~-的分光光度测定。其表观克分子吸收系数在3,409—3,478,也可     

2.5次微分电分析法直接测定NO_3~-离子的研究

极谱法测定NO_3~-离子,人们研究较多的是先将NO_3~-离子还原为NO_2~-,然后借助催化体系通过测定NO_2~-离子来换算NO_3~-的含量。近来,直接测定NO_3~-离子也有报道,在硫酸钾的存在下,利用硝酸根与铀离子的催化反应,以微分脉冲极谱法测定NO_3~-离子的含量。但NO_2~-,HPO_4~(2-)离子干扰严重,必须预先除去。本文通过实验,发现在醋酸铀酞-尿素体系中,大量的NO_2~-离子存在,不干扰NO_3~-的直接测定。应用该法测定了四种天然水样品,测定结果及回收率均较为满意。     

镉屑还原-偶氮染料比色法测定水中NO_3~-

本文仅用镉屑作还原剂,把NO_3~-还原成NO_2~-,以偶氮染料比色法定量。方法简便、快速,对环境污染小,干扰少。时NO_3~-测定范围为0.04—1.3 ppm,检出限为0.030 ppm。精密度、准确度较好,适于地面水、降水中NO_3~-的测定。     

紫外辐照法合成环蕃醛

利用254 nm紫外光对[2.2]对环蕃氯仿溶液进行辐照,得到两种主要产物4-醛基-[2.2]-对环蕃和4,4'-(乙基-1,2-二取代)二苯甲醛,利用核磁共振波谱仪(NMR)和气相色谱-质谱联用(GC-MS)技术手段对产物的结构进行分析研究。 同时对反应条件进行探究,发现当氯仿和水同时存在时才能生成醛基,并由此提出了提出了可能的反应机理:通过瑞默-提曼反应使CHCl₂·自由基加成到苯环上并进一步生成醛基。     

紫外光照还原-流动注射分光光度法测定海水中硝酸盐

在pH 8.2的二乙三胺五乙酸-三羟甲基氨基甲烷(DTPA-Tris)缓冲介质中,通过紫外光照射使NO3-还原为NO2-后,与显色剂反应生成吸收峰位于540 nm波长处的化合物,据此提出了在线紫外光照还原流动注射分光光度法测定海水中硝酸盐。经试验,选择30 g·L-1氯化钠溶液作为载流,所选定的反应圈及样品环的长度依次为180 mm和130 mm。硝酸盐的质量浓度在0.009~3.0 mg·L-1范围内与相应的吸光度呈线性关系,其检出限(3s/k)为4.63μg·L-1。对同一天然海水样品按此法测定其NO3-含量10次,测得其平均值为0.538 mg·L-1,相对标准偏差为0.34%,并求得NO3-的还原率为80%。另在6个海水样品中各加0.50 mg·L-1NO3-标准溶液,按方法做回收试验,测得其回收率在97%以上。     

Crystallization and Reduction of Sol-Gel-Derived Zinc Oxide Films by Irradiation with Ultraviolet Lamp

Structural changes in sol-gel films with photo-irradiation were investigated using zinc oxide (ZnO) derived from zinc acetate. The exposure of the films to an ultraviolet lamp induced hexagonal ZnO crystals in a relatively dense amorphous structure. On the other hand, the formation of zinc metal was found in a porous gel film. The photo-induced crystallization and reduction are ascribed to the electronic excitation in the metastable non-crystalline states.     

紫外线辐照制备单分散ZnS纳米颗粒

以硫代硫酸钠和乙酸锌为反应物、柠檬酸为调控剂,在紫外光辐照下制备出单分散的ZnS纳米颗粒。采用XRD、TEM、低温氮吸附-脱附、HRTEM和EDS等方法研究了反应物浓度、辐照时间和柠檬酸用量等因素对产物颗粒尺寸和分布的影响。结果表明,随着反应时间延长,产物收率增高,平均晶粒度增大,比表面积变小。反应物浓度对产物组成和比表面积有较大影响,但对产物的平均晶粒度影响不大。适量添加柠檬酸,有利于制备单分散的ZnS纳米颗粒。     

Ultraviolet Spectroscopic Detection of Nitrate and Nitrite in Seawater Simultaneously Based on Partial Least Squares

A direct, reagent-free, ultraviolet spectroscopic method for the simultaneous determination of nitrate (NO₃⁻), nitrite (NO₂⁻), and salinity in seawater is presented. The method is based on measuring the absorption spectra of the raw seawater range of 200–300 nm, combined with partial least squares (PLS) regression for resolving the spectral overlapping of NO₃⁻, NO₂⁻, and sea salt (or salinity). The interference from chromophoric dissolved organic matter (CDOM) UV absorbance was reduced according to its exponential relationship between 275 and 295 nm. The results of the cross-validation of calibration and the prediction sets were used to select the number of factors (4 for NO₃⁻, NO₂⁻, and salinity) and to optimize the wavelength range (215–240 nm) with a 1 nm wavelength interval. The linear relationship between the predicted and the actual values of NO₃⁻, NO₂⁻, salinity, and the recovery of spiked water samples suggest that the proposed PLS model can be a valuable alternative method to the wet chemical methods. Due to its simplicity and fast response, the proposed PLS model can be used as an algorithm for building nitrate and nitrite sensors. The comparison study of PLS and a classic least squares (CLS) model shows both PLS and CLS can give satisfactory results for predicting NO₃⁻ and salinity. However, for NO₂⁻ in some samples, PLS is superior to CLS, which may be due to the interference from unknown substances not included in the CLS algorithm. The proposed method was applied to the analysis of NO₃⁻, NO₂⁻, and salinity in the Changjiang (Yangtze River) estuary water samples and the results are comparable with that determined by the colorimetric Griess assay.     

流动注射-毛细管电泳直接紫外测定环境水中硝酸根和亚硝酸根

采用流动注射与毛细管电泳联用（FI-CE）接口进行自动连续采样。对检测波长、电渗流改性剂浓度、载流中四硼酸钠浓度、载流PH、载流流速及采样环体积等条件进行优化，并对环境水样中常见阴离子的干扰进行研究，建立了同时测定水中硝酸根和亚硝酸根的方法。在采样量为50μl时硝酸根和亚硝酸根的检出限（3σ）分别为0.2和0.4mg/L；峰高RSD分别为1.6%和2.0%(20mg/L,n=25)，峰面积RSD分别为1.7%和1.6%(20mg/L,n=25)，采样频率为60/h。用本法测定井水水样的结果与离子色谱法一致。水样中加入10mg/L硝酸根和亚硝酸根的回收率为98%-108%。     

比光谱-导数-紫外分光光度法同时测定水中硝酸根和亚硝酸根

利用二元混合物的混合光谱与其中某一组分光谱的比值对波长求导，可达到分辨重叠光谱的目的。本文研究了用比光谱-导数-紫外分光光度法同时测定水样中NO3-和NO2-，以“减法技术”求导，兼具导数光度法能消除低频背景和高频噪声干扰及线性回归法分辨能力强的优点。方法避免了一般光度法需加入试剂而可能引起的误差。在pH7～9条件下测量203um～219um的光吸收值，用比光谱-导数技术处理，同时测定合成试样中0～4mg／L的NO3-和NO2-，6次测定相对标准偏差＜7％，加入回收率在95％～101％之间。讨论了干扰离子的影响及消除，并与P-矩阵法作了比较。方法已用于井水、雨水及湖水中NO3-和NO2-的同时测定。     

A Spectroscopic Study of Electrochemical Nitrogen and Nitrate Reduction on Rhodium Surfaces

Rh is a promising electrocatalyst for the nitrogen reduction reaction (NRR) given its suitable nitrogen‐adsorption energy and low overpotential. However, the NRR pathway on Rh surfaces remains unknown. In this study, we employ surface‐enhanced infrared‐absorption spectroscopy (SEIRAS) and differential electrochemical mass spectrometry (DEMS) to study the reaction mechanism of NRR on Rh. N₂H_x (0≤x≤2) is detected with a N=N stretching mode at ≈2020 cm^?1 by SEIRAS and a signal at m/z=29 by DEMS. A new two‐step reaction pathway on Rh surfaces is proposed that involves an electrochemical process with a two‐electron transfer to form N₂H₂ and its subsequent decomposition in the electrolyte producing NH₃. Our results also indicate that nitrate reduction and the NRR share the same reaction intermediate N₂H_x.     

A Turbidity-Compensation Method for Nitrate Measurement Based on Ultraviolet Difference Spectroscopy

To solve the problem that turbidity in water has a significant effect on the spectra of nitrate and reduces the accuracy of nitrate detection, a turbidity-compensation method for nitrate measurement based on ultraviolet difference spectra is proposed. The effect of turbidity on the absorption spectra of nitrate was studied by using the difference spectra of the mixed solution and a nitrate solution. The results showed that the same turbidity had different effects on the absorbance of different concentrations of nitrate. The change in absorbance due to turbidity decreased with an increase in the nitrate concentration at wavelengths from 200 nm to 230 nm, although this change was constant when the wavelength was greater than 230 nm. On the basis of this characteristic, we combined the residual sum of squares (RSS) and interval partial least squares (iPLS) to select wavelengths of 230–240 nm as the optimal modeling interval. Furthermore, the turbidity-compensation model was established by the linear fitting of the difference spectra of various levels of turbidity. The absorption spectra of the nitrate were extracted by subtracting the turbidity-compensation curve from the original spectra of the water samples, and the nitrate concentration was calculated by using a partial least squares (PLS)-based nitrate-prediction model. The experimental results showed that the average relative error of the nitrate predictions was reduced by 50.33% to 1.33% by the proposed turbidity-compensation method. This indicated that this method can better correct the deviation in nitrate’s absorbance caused by turbidity and improve the accuracy of nitrate predictions.