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91.
J. Howard Rytting Danny R. McHan Takeru Higuchi David J. W. Grant 《Journal of solution chemistry》1986,15(8):693-703
Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G
2
0
of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G
2
0
decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G
2
0
against the change in pair potential energy calculated from the classical expressions suggests that G
2
0
seriously underestimates the strength of the Debye interactions in comparison with the London interactions. 相似文献
92.
丙烯选择氧化铋钼铁复氧化物催化剂组成,结构及性能的研究 总被引:1,自引:0,他引:1
采用XRD、Raman、XPS及催化剂性能评价等手段,考察了Bi_3(FeO_4)(MoO_4)_2和Fe_2(MoO_4)_3分别存在及两者共存时对Bi-Mo复氧化物体系催化性能的影响.结果表明,这两种含Fe物种的存在都有助于改善Bi-Mo系复氧化物催化剂对丙烯选择氧化反应的催化性能.但两者在作用机理上有所不同.Fe_2(MoO_4)_3本身无催化活性,但在反应条件下可部分还原为FeMoO_4形成Fe~(3+)/Fe~(2+)氧化还原对;且其地结构上与α-Bi_2(MoO_4)_3相匹配,这些因素都有助于促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生,从而提高催化性能.Bi_3(FeO_4)(MoO_4)_2在反应条件下也可形成Fe~(3+)/Fe~(2+)氧化还原对,但由于其Fe~(3-)所处的化学环境与Fe_2(MoO_4)_3很不相同,且Fe的含量也不及Fe_2(MoO_4)_3,因此它在促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生等方面的性能较差,但它对提高催化剂表面的活性中心(Bi-Mo对)数目有贡献. 相似文献
93.
94.
95.
96.
Li-Juan Jia Yuan-Yuan Wang Hui Chen Yong-Kui Shan Li-Yi Dai 《Reaction Kinetics and Catalysis Letters》2005,86(2):267-273
Summary The alkylation of benzene with 1-hexene has been investigated in different triethylamine hydrochloride-ferric chloride (Et3NHCl-FeCl3) and triethylamine hydrochloride-aluminium chloride (Et3NHCl-AlCl3) ionic liquids. Both high catalyst activity and monoalkylation selectivity were observed for these two type of ionic liquids.
Systems prepared by modification with HCl in Et3NHCl-FeCl3ionic liquids prove to be very suitable solvents and catalysts for the reaction. When employing Et3NHCl-AlCl3ionic liquids as catalysts, the reaction takes place in biphasic mode with facile catalyst separation and catalyst recycling. 相似文献
97.
气相色谱质谱联用仪与微机的数据传输和处理 总被引:1,自引:0,他引:1
报道了一种用于气相色谱质谱联用仪和微机之间实现数据传输和处理的方法。方法可更有效地利用质谱仪采集的数据,解决了工作站处理数据的局限性。经数据格式转换,原始数据可以在微机上实现色谱峰再现,从而为色谱条件的优化和定量数据处理创造了条件。 相似文献
98.
Hong Tao Gao Dong Mei Dai Tong Hua Li 《中国化学快报》2007,18(4):495-498
Non-negative matrix factorization(NMF)is a technique for dimensionality reduction by placing non-negativity constraints onthe matrix.Based on the PARAFAC model,NMF was extended for three-dimension data decomposition.The three-dimension non-negative matrix factorization(NMF3)algorithm,which was concise and easy to implement,was given in this paper.The NMF3algorithm implementation was based on elements but not on vectors.It could decompose a data array directly without unfolding,which was not similar to that the traditional algorithms do.It has been applied to the simulated data array decomposition andobtained reasonable results.It showed that NMF3 could be introduced for curve resolution in chemometrics. 相似文献
99.
The photochemistry of 13 4,4-diphenylcyclohexenones, substituted at carbon-6, was investigated in solution and in the crystalline state. The stereoselectivity was of particular interest. In the solution photochemistry of C-6 monosubstituted enones in benzene, there was a unique preference for migration of the cis-phenyl group with formation of bicyclo[3.1.0]hexanone photoproducts, with the original 6-substituent having an endo configuration at carbon-3 of the product. In methanol the reaction was diverted to afford 3,4-diphenylcyclohex-2-enes understood as arising from a hydrogen-bonded zwitterionic intermediate. The solid-state photochemistry was also investigated. There was a dramatic absence of the 3,4-diphenylcyclohex-2-ene products in accord with the absence of the hydrogen bonding encountered in methanol. Further, the solid-state reactivity correlated with a vector analysis using X-ray atomic coordinates. This established that the migrating phenyl group required an orientation facing the enone beta-carbon. While the interesting preference for the cis-endo migration was not intuitively predicted, ab initio computations on the alternative phenyl-bridged triplet intermediates did lead to an understanding of the selectivity. 相似文献
100.
The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1–aminopyrene and pmpa=N–(2–pyridylmethylene)–1–pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, esták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献