【摘要】：磷作為水生物生長(zhǎng)不可缺少的物質(zhì),在整個(gè)生物過程扮演很重要的角色。水中所含磷的濃度決定著水體質(zhì)量,太高會(huì)使得藻類瘋長(zhǎng)甚至導(dǎo)致富營養(yǎng)化。隨著經(jīng)濟(jì)的不斷發(fā)展,大量未經(jīng)處理的工農(nóng)業(yè)污水被直接排入河水中,使得總磷濃度超過了標(biāo)準(zhǔn)含量,導(dǎo)致水污染甚至危害著動(dòng)植物的生存。因此準(zhǔn)確監(jiān)測(cè)水中總磷濃度及時(shí)控制磷含量成為水環(huán)境保護(hù)的首要任務(wù)。離子選擇電極具有選擇性好、操作簡(jiǎn)單、成本效益高而且易小型化、適合實(shí)時(shí)測(cè)量等優(yōu)點(diǎn),并逐漸被大量用于測(cè)量磷酸鹽濃度的研究。本文在敏感物質(zhì)金屬鉬的基礎(chǔ)上開發(fā)了一種新型電極,并用于磷的測(cè)量,主要研究成果如下:(1)研究了一種基于鉬的磷酸根離子選擇電極,電極測(cè)量磷酸一氫根(2-4HPO)的原理是通過鉬在堿性條件下與2-4HPO反應(yīng)來實(shí)現(xiàn)的。實(shí)驗(yàn)結(jié)果顯示鉬電極在溶液pH值為8.5條件下對(duì)磷酸氫二鈉(42HPONa)在/10-10Lmol1-5-線性范圍內(nèi)響應(yīng)斜率可以達(dá)到?/5.026.9-decm V(近能斯特Nernst斜率);檢測(cè)下限達(dá)到/109.1Lmol-6?;響應(yīng)時(shí)間小于50s;在連續(xù)測(cè)量中響應(yīng)電位標(biāo)準(zhǔn)偏差為2mV;在不同濃度待測(cè)溶液的往復(fù)測(cè)量中電位標(biāo)準(zhǔn)偏差均小于2m V;而且除了-OH對(duì)測(cè)量有一定的影響外,鉬電極對(duì)2-4HPO有很好的選擇性。測(cè)量數(shù)據(jù)顯示該電極至少可以使用三個(gè)月。電極制造工藝簡(jiǎn)單而且廉價(jià),適用于水中磷酸鹽的定量分析。(2)根據(jù)2-4HPO離子濃度(即磷酸鹽分布系數(shù))以及鉬電極測(cè)量電位所受p H的影響,將分布系數(shù)和p H線性補(bǔ)償項(xiàng)引入Nernst方程,建立磷酸根離子選擇電極的測(cè)量模型,以克服p H對(duì)電極測(cè)量的影響。實(shí)驗(yàn)結(jié)果顯示電極對(duì)42HPONa溶液在2-4HPO對(duì)應(yīng)/10-10Lmol-1-6的線性范圍內(nèi)響應(yīng)斜率可以達(dá)到/5.032.24-?decm V,檢測(cè)下限達(dá)到/1017.1Lmol-6?,并表現(xiàn)出很好的線性響應(yīng)特性。電極能滿足磷酸鹽離子的測(cè)量要求,可以用于實(shí)際水樣中磷含量的在線監(jiān)測(cè)。(3)針對(duì)傳統(tǒng)總磷在線分析技術(shù)測(cè)量復(fù)雜且需要昂貴設(shè)備和使用化學(xué)試劑等缺點(diǎn),研究采用實(shí)驗(yàn)室已有的基于3/OUV的氧化消解技術(shù)與基于鉬的磷酸根離子選擇電極相結(jié)合來解決,通過建立的模型優(yōu)化測(cè)量效果。實(shí)驗(yàn)發(fā)現(xiàn)基于3/OUV的氧化消解技術(shù)消解后的溶液主要呈現(xiàn)酸性,不滿足鉬電極的堿性測(cè)量要求,需要采用電解自來水來調(diào)節(jié)消解溶液p H值。實(shí)驗(yàn)結(jié)果顯示p H調(diào)節(jié)的高低對(duì)電極的測(cè)量效果有很大的影響,需要根據(jù)實(shí)際測(cè)量需求選擇p H的調(diào)節(jié)值,當(dāng)pH值調(diào)節(jié)整體高于7.5的情況下,電極在/109.7-1068.2Lmol-5-6??范圍內(nèi)達(dá)到/5.026.092-?decm V的近Nernst斜率,檢測(cè)下限為/1068.2Lmol6-?;pH值調(diào)節(jié)整體低于7后,電極響應(yīng)斜率降低為/0.524.622-?decm V,但線性范圍變寬到/101.01-101.14Lmol-4-6??,檢測(cè)下限也隨之降低到/1014.1Lmol-6?。與此同時(shí),實(shí)驗(yàn)發(fā)現(xiàn)p H調(diào)節(jié)在不同濃度下添加的電解自來水體積不同,需要依據(jù)溶液p H值來決定。
[Abstract]:Phosphorus, as an indispensable substance for the growth of aquatic organisms, plays an important role in the whole biological process. The concentration of phosphorus in the water determines the quality of the water, too high will cause algae to grow and even lead to eutrophication. With the continuous development of economy, a large number of untreated industrial and agricultural sewage is discharged directly into the river water, which makes the total phosphorus concentration exceed the standard content, leading to water pollution and even endangering the survival of animals and plants. Therefore, accurate monitoring of total phosphorus concentration in water and timely control of phosphorus content has become the primary task of water environmental protection. Ion selective electrode has many advantages such as good selectivity, simple operation, high cost benefit and easy miniaturization. It is suitable for real-time measurement and has been widely used in the study of phosphate concentration measurement. In this paper, a new type of electrode has been developed on the basis of molybdenum, which has been used in the measurement of phosphorus. The main results are as follows: (1) A kind of phosphate ion selective electrode based on molybdenum has been studied. The principle of electrode measurement of monohydrogen phosphate (2-4HPO) is achieved by the reaction of molybdenum with 2-4HPO in alkaline condition. The experimental results show that the molybdenum electrode has a slope of? / 5.026.9-decm V (near Nast Nernst slope) in the linear range of / 10-10 Lmol1-5- to sodium hydrogen phosphate (42HPONa) when the solution pH value is 8.5. The detection limit reached / 109.1 Lmol-6, the response time was less than 50 s, the standard deviation of response potential was 2 MV in continuous measurement, and the standard deviation of potential in reciprocating measurement of different concentrations of solution was less than 2m V. Besides-OH, molybdenum electrode has good selectivity to 2-4HPO. Measurements show that the electrode can be used for at least three months. The electrode manufacturing process is simple and cheap, which is suitable for quantitative analysis of phosphate in water. (2) according to the concentration of 2-4HPO ion (i.e. phosphate distribution coefficient) and the influence of pH on the potential measured by molybdenum electrode, The distribution coefficient and pH linear compensation term are introduced into Nernst equation to establish the measurement model of phosphate ion selective electrode to overcome the influence of pH on electrode measurement. The experimental results show that the response slope of the electrode to 42HPONa solution can reach / 5.032.24-?decm V in the linear range of 2-4HPO / 10-10Lmol-1-6, and the detection limit reaches / 1017.1 Lmol-6. It also shows good linear response characteristics. The electrode can meet the requirements of phosphate ion measurement and can be used for on-line monitoring of phosphorus content in real water samples. (3) in view of the disadvantages of traditional on-line total phosphorus analysis technology such as complex measurement and expensive equipment and the use of chemical reagents. In this study, the existing oxidation digestion technology based on 3/OUV and the molybdenum based phosphate ion selective electrode were used to solve the problem, and the measurement results were optimized by the established model. It was found that the solution after digestion based on 3/OUV was mainly acidic and could not meet the requirement of alkaline measurement of molybdenum electrode. Electrolytic tap water was needed to adjust pH value of digestion solution. The experimental results show that the pH regulation has a great influence on the measuring effect of the electrode. It is necessary to select the pH adjustment value according to the actual measurement demand. When the pH value is higher than 7.5, Electrode at / 109.7-1068.2 Lmol-5-6? In the range of / 5.026.092-?decm V, the near Nernst slope was reached, and the detection limit was / 1068.2 Lmol 6-buff; When the pH value is lower than 7, the electrode response slope is reduced to / 0.524.622-?decm V, but the linear range is widened to / 101.01-101.14Lmol-4-6, and the detection limit is reduced to / 1014.1 Lmol-6. At the same time, it was found that the volume of electrolytic tap water added with different concentration of pH was different, which should be determined by pH value of solution.
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.1

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