本文關(guān)鍵詞：大氣中有機(jī)酸強(qiáng)化均相核化機(jī)制的理論研究　出處：《山東大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 新粒子生成 密度泛函理論 有機(jī)酸 丙二酸 富馬酸

【摘要】：大氣中新粒子生成機(jī)制和增長(zhǎng)特性的研究對(duì)于理解區(qū)域空氣污染和全球氣候變化具有十分重要的意義,但到目前為止,沒有一種完善的核化理論能夠完美解釋大氣新粒子生成機(jī)制。盡管大氣氣溶膠中已被證明含有有機(jī)成分,但有機(jī)酸參與成核的化學(xué)本質(zhì)和物理化學(xué)過程仍不清楚。本論文對(duì)常見有機(jī)酸成核效率進(jìn)行對(duì)比確認(rèn)了催化成核能力強(qiáng)的物種,并研究了其在大氣中強(qiáng)化均相核化的機(jī)制,為加深對(duì)有機(jī)物參與成核機(jī)制的理解提供參考。本論文采用量子化學(xué)密度泛函理論,在PW91PW91/6-311++G(3df,3pd)水平上計(jì)算,得到以下有意義的研究結(jié)果：(1)對(duì)甲酸、乙酸等大氣中14種常見的有機(jī)酸參與成核的效率進(jìn)行了對(duì)比,發(fā)現(xiàn)這14種有機(jī)酸與硫酸形成二聚體的穩(wěn)定性大多接近或超過了硫酸-硫酸二聚體,其中丁二酸、苯甲酸、苯乙酸、乙酸與硫酸形成的二聚體最穩(wěn)定。甲酸等14種有機(jī)酸與氨氣、有機(jī)胺形成的二聚體不如硫酸-氨氣／有機(jī)胺穩(wěn)定,但有機(jī)酸、有機(jī)胺等在大氣中濃度較高,能形成穩(wěn)定分子團(tuán)簇并參與較大的復(fù)雜多組分分子團(tuán)簇形成。通過對(duì)甲酸等十四種常見的有機(jī)酸、硫酸與氨氣／甲胺/二甲胺形成穩(wěn)定分子團(tuán)簇的效率進(jìn)行比較,確定了丙二酸、丁二酸和富馬酸是對(duì)這些有機(jī)酸-硫酸-氨氣／有機(jī)胺分子團(tuán)簇穩(wěn)定效果最明顯的有機(jī)酸。(2)丙二酸、富馬酸與有機(jī)胺成核效率低于硫酸-有機(jī)胺。水化作用會(huì)降低丙二酸、富馬酸對(duì)有機(jī)胺反應(yīng)活性,但能提高有機(jī)胺對(duì)這兩種有機(jī)酸的反應(yīng)活性。丙二酸-二甲胺成核效率高于丙二酸-甲胺成核效率。丙二酸和富馬酸對(duì)二甲胺的穩(wěn)定效果相近,丙二酸在大氣中濃度通常高于富馬酸,因此丙二酸對(duì)穩(wěn)定有機(jī)胺形成穩(wěn)定團(tuán)簇的貢獻(xiàn)大于富馬酸。(3)丙二酸、富馬酸對(duì)大氣中多組分成核具有顯著的強(qiáng)化效果,且兩種有機(jī)酸對(duì)二甲胺參與的多組分成核催化效率更高。從熱力學(xué)角度,丙二酸和富馬酸在大氣中更傾向于與有機(jī)胺形成穩(wěn)定水化分子團(tuán)簇,協(xié)同催化硫酸成核。
[Abstract]:Study on the formation mechanism and growth characteristics of new particles in the atmosphere is of great significance for understanding the regional air pollution and global climate change, but so far, not a perfect nucleation theory can perfectly explain the atmospheric new particle formation mechanism. Although the atmospheric aerosol has been shown to contain organic ingredients, but the organic acid in the chemical and physical and chemical nature of nuclear process remains unclear. In this paper, the common organic acid nucleating efficiency comparison confirmed the catalytic nucleation ability of the species, and to study the enhancement of homogeneous nucleation mechanism in the atmosphere, in order to enhance and provide reference for organic compounds are involved in nucleation mechanism understanding. This thesis is based on the quantum chemical density functional theory, the PW91PW91/6-311++G (3DF, 3pd) on the level of calculation, get the following significant research results: (1) of formic acid, acetic acid in the atmosphere of 14 kinds of common organic Acids are involved in nucleation efficiency were compared, found that 14 kinds of organic acid and sulfuric acid to form two dimer stability are close to or more than two sulfuric acid dimer, including succinic acid, benzoic acid, phenylacetic acid, acetic acid and sulfuric acid to form two dimer is the most stable. 14 kinds of organic acid and formic acid ammonia, organic amine formed two dimers as sulfuric acid and ammonia / organic amine is stable, but the organic acid, organic amine concentration in the atmosphere is higher, can form stable clusters and participate in more complex multicomponent molecular clusters. The acid fourteen kinds of organic acid, comparison the efficiency of sulfuric acid and ammonia / methylamine / two methylamine to form stable molecular clusters, the malonic acid, succinic acid and fumaric acid is the stabilizing effect of these organic acid - sulfuric acid ammonia / organic amine molecular clusters. The most obvious organic acid (2) malonic acid, fumaric acid and organic amine into Nuclear efficiency is lower than the sulfuric acid and organic amine. The hydration will reduce malonic acid, fumaric acid in organic amine reaction activity, but can increase the reaction activity of organic amine on the two kinds of organic acid. Malonic acid - two methylamine nucleation efficiency is higher than that of malonic acid - methylamine nucleation efficiency. Stable effect of malonic acid and fumaric acid on a two amine similar, malonic acid concentration in the atmosphere is usually higher than the fumaric acid, malonic acid to form stable clusters of stable organic amine contributed more than fumaric acid. (3) malonic acid, fumaric acid in the atmosphere of the multispecies nucleus had significant enhancement effect, and two kinds of organic acids in higher catalytic efficiency into nuclear group two different participation. From the view of thermodynamics, malonic acid and fumaric acid in the atmosphere tends to form a stable water molecular cluster and organic amine sulfate, synergistic catalytic nucleation.

【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X513

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