Interactions of sulfuric acid with common atmospheric bases and organic acids: Thermodynamics and implications to new particle formation

Interactions of the three common atmospheric bases, dimethylamine ((CH₃)₂NH), methylamine (CH₃NH₂), ammonia (NH₃), all considered to be efficient stabilizers of binary clusters in the Earth's atmosphere, with H₂SO₄, the key atmospheric precursor, and 14 common atmospheric organic acids (COAs) (formic, acetic, oxalic, malonic, succinic, glutaric acid, adipic, benzoic, phenylacetic, pyruvic, maleic acid, malic, tartaric and pinonic acids) have been studied using the density functional theory (DFT) and composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA)(H₂SO₄), (COA)(B1), (COA)(B2) and (COA)(B3) dimers and (COA)(H₂SO₄)(B1), (COA)(H₂SO₄)(B2) and (COA)(H₂SO₄)(B3) trimers, where B1, B2 and B3 refer to (CH₃)₂NH, CH₃NH₂ and NH₃, respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H₂SO₄ have been studied. Our investigation shows that interactions of H₂SO₄ with COA, (CH₃)₂NH, CH₃NH₂ and NH₃ lead to the formation of more stable mixed dimers and trimers than (H₂SO₄)₂ and (H₂SO₄)₂(base), respectively, and emphasize the importance of common organic species for early stages of atmospheric nucleation. We also show that although amines are generally confirmed to be more active than NH₃ as stabilizers of binary clusters, in some cases mixed trimers containing NH₃ are more stable thermodynamically than those containing CH₃NH₂. This study indicates an important role of COA, which coexist and interact with that H₂SO₄ and common atmospheric bases in the Earth atmosphere, in formation of stable pre-nucleation clusters and suggests that the impacts of COA on new particle formation (NPF) should be studied in further details.     

Comparison of exergy found by a classical thermodynamic approach and by the use of the information stored in the genome

It is possible to calculate the exergy for organisms based on classic thermodynamics as already demonstrated by Mejer and Jorgensen [Mejer, H., Jorgensen, S.E., 1979. Exergy and ecological buffer capacity. State-of-the-art in Ecol. Model. 7, 829–846]. The calculation of exergy as eco-exergy, which is based on the information stored in the genome, has lately been proposed by Jørgensen and co-workers. Recently, Ludovisi [Ludovisi, A., 2009. Exergy vs information in ecological successions: interpreting community changes by a classical thermodynamic approach. Ecol. Model. 220, 1566–1577] has put forward a method based on classical thermodynamics, which leads to the calculation of “virtual” values of concentration at equilibrium for a number of organic compounds (VEC) and freshwater organisms (VECE). This paper compares the two approaches by analysing the correlation existing between the VECE- and the β-values derived by Jørgensen et al. [Jørgensen, S.E., Ladegaard, N., Debeljak, M., Marques, J.C., 2005. Calculations of exergy for organisms. Ecol. Model. 185, 165–175]. It was found that there was a good correlation, which can be useful for estimating β-values for organisms whose genome is not known in a sufficient detail. The relationship between VECE- and β-values suggests that two proposed thermodynamic orientors based on these quantities – the eco-exergy index and the structural information – should lead to coherent results when applied to the evaluation of the development state of ecosystems. A numerical simulation shows that this expectation is verified in a major case, but also that different, even opposite, responses can arise, depending on the biological composition of the biocoenosis investigated.     

NaClO_2碱性溶液脱硝的热力学计算与实验研究

液相氧化脱硝技术被认为是最有前景的脱硝技术之一。在自制的鼓泡反应器中,进行NaClO2/NaOH溶液脱硝实验。热力学计算表明,300~380K,脱硝反应是放热反应,反应的平衡系数均非常大,但随温度的升高而减小。选取吸收时间、NaClO2浓度、初始、反应温度、模拟烟气流量以及烟气中pHNO含量为过程参数,脱硝率作为响应量,分别进行了单因素实验。结果表明:脱硝率随NaClO2浓度、反应温度的增加而升高,随吸收时间、烟气流量或NO含量的增加而降低,在pH7~10范围内,体系获得较好的脱硝效果;NaClO2浓度,初始0.02mol/LpH,10温度70℃,烟气流量0.4L/min的条件下,处理NO含量0.02%~0.05%范围内的烟气,吸收20min内体系脱硝率几乎为100%。