本文選題：有機(jī)胺 + 反應(yīng)機(jī)理　； 參考：《東北師范大學(xué)》2017年碩士論文

【摘要】：在大氣污染化學(xué)中,亞硝酸(HONO)與含氮顆粒物同為典型的二次污染物,兩者密不可分。亞硝酸被認(rèn)為是重要的對(duì)流層的痕量氣體,它可以經(jīng)過(guò)光照分解而釋放大量的OH自由基。盡管亞硝酸的重要性已經(jīng)被意識(shí)到,但是對(duì)于它的來(lái)源及其形成的化學(xué)機(jī)理,還沒(méi)有得到很好地認(rèn)識(shí)和理解。本文研究了甲胺和二甲胺對(duì)二氧化氮水解反應(yīng)的影響,并與氨氣進(jìn)行對(duì)比。通過(guò)量子化學(xué)理論計(jì)算了一系列分子簇,包括2NO_2-mH_2O-CH_3NH_2(m=1-3)和2NO_2-mH_2O-(CH_3)_2NH(m=1,2)。具體反應(yīng)過(guò)程如下:2NO_2(g)+ mH_2O(g)+ CH_3NH_2(g)→Products(m=1-3)2NO_2(g)+ mH_2O(g)+(CH_3)_2NH(g)→Products(m=1,2)結(jié)果表明,在二氧化氮水解反應(yīng)過(guò)程中,甲胺和二甲胺比氨氣具有更大的熱力學(xué)影響。反應(yīng)中增加的水分子不僅可以穩(wěn)定過(guò)渡態(tài)和產(chǎn)物復(fù)合物,并且能促進(jìn)硝酸鹽的形成。當(dāng)分子簇中存在甲胺時(shí),反應(yīng)過(guò)程中的能壘降低了3.2 kcal mol-1,產(chǎn)物復(fù)合物更加穩(wěn)定。在硝酸的水合作用中,甲胺和二甲胺也比氨氣具有更大的影響,隨著水分子的增加,物質(zhì)NH4NO3,CH_3NH_3NO3和(CH_3)_2NH_2NO3都傾向于形成更大的氣溶膠分子。同時(shí),本文也研究了復(fù)合物HONO-CH_3NH_2和HONO-NH_3的平衡結(jié)構(gòu),諧波振動(dòng)頻率和強(qiáng)度。計(jì)算結(jié)果表明,復(fù)合物HONO-CH_3NH_2的結(jié)合能均強(qiáng)于HONO-NH_3復(fù)合物,OH伸縮振動(dòng)頻率和強(qiáng)度是受復(fù)合物形成的影響最大的。給受體間作用的NBO分析結(jié)果表明,在甲胺和二甲胺存在下的分子簇間的相互作用要大于氨氣存在的情況,復(fù)合物HONO-CH_3NH_2中存在更大的二階穩(wěn)定化能。
[Abstract]:In atmospheric pollution chemistry, HONO2 and N-containing particulates are typical secondary pollutants, which are closely related to each other. Nitrite is considered to be an important tropospheric trace gas, which can release a large amount of OH free radicals by light decomposition. Although the importance of nitrite has been recognized, its source and the chemical mechanism of its formation have not been well understood and understood. The effects of methylamine and dimethylamine on the hydrolysis of nitrogen dioxide were studied and compared with ammonia. A series of molecular clusters have been calculated by quantum chemistry theory, including 2NOS _ 2mH _ 2O-CH3NH _ 2T _ 2M _ 3) and 2NO _ 2-mH _ 2O-T _ 2H _ 2O-T _ 2NH _ m _ 3. The specific process of the reaction is as follows: 2NO2G) mH2Og) Ch 3NH / 2G) Productsm (1 / 3N / 2NO2G) / mH2Og) the results show that methylamine and dimethylamine have a greater thermodynamic effect than ammonia in the process of the hydrolysis of nitrogen dioxide by means of the following steps: CH3NO2G) / mH2OG) / Ch _ 3NO2G) / D _ 2N _ 2H _ 2H _ 2O _ 2g)] the results show that during the hydrolysis of nitrogen dioxide, methylamine and dimethylamine have a greater thermodynamic effect than ammonia in the process of hydrolysis of nitrogen dioxide. The addition of water molecules can not only stabilize the transition state and product complex, but also promote the formation of nitrate. When methylamine is present in the molecular cluster, the energy barrier decreases by 3.2 kcal mol-1 during the reaction, and the product complex is more stable. In the water cooperation of nitric acid, methylamine and dimethylamine also have more influence than ammonia. With the increase of water molecule, the substance NH _ 4NO _ 3 / C _ 3NH _ 3NO _ 3 and Ch _ 3s _ 2NH _ 3NO _ 3 are all inclined to form larger aerosol molecules. At the same time, the equilibrium structure, harmonic vibration frequency and intensity of the composite HONO-CH3NH _ 2 and HONO-NH3 are also studied. The results show that the binding energy of HONO-CH3NH2 is stronger than that of HONO-NH3 complex. The frequency and intensity of OH stretching vibration of HONO-CH3NH2 complex are the most affected by the formation of the complex. The results of NBO analysis for the interaction between the receptors show that the interaction between the clusters in the presence of methylamine and dimethylamine is greater than that in the presence of ammonia, and there is a greater second order stabilization energy in the complex HONO-CH3NHStack2.
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O643.12

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