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51.
Rabindra N. Roy Lakshmi N. Roy Jason G. Grant Mason P. Cummins Bennett J. Tabor III Sarah J. Richards Curtis A. Himes Bret R. Lively Penny L. Blackwell Ashley N. Simon 《Journal of solution chemistry》2002,31(11):861-872
The values of the second dissociation constant, pK
2, for the dissociation of the NH+ charge center of the zwitterionic buffer compounds 4-(N-morpholino)butanesulfonic acid (MOBS), and N-(2-hydroxyethyl)piperazine-N-4-butanesulfonic acid (HEPBS) have been determined from 5 to 55°C, including, 37°C at intervals of 5°C. The electromotive-force (emf) measurements have been made utilizing hydrogen electrodes and silver–silver chloride electrodes. The value of pK
2 for MOBS was found to be 7.702 ± 0.0005, and 8.284 ± 0.0004 for HEPBS, at 25°C, respectively. The related thermodynamic quantities, G
o, H
o, S
o, and C
p
o for the dissociation processes of MOBS and HEPBS have been derived from the temperature coefficients of pK
2. Both the MOBS and HEPBS buffer materials are useful as primary pH standards for the control of pH 7.3 to 8.6 in the region close to that of physiological fluids. 相似文献
52.
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
53.
54.
1 INTRODUCTION Ionic compounds generally have high melting points and always exist in solid state since they are main- tained by electrovalent bonds. Ionic Liquids (ILs), which are liquids at or near ambient temperature, have been a class of ionic compounds extensively studied experimentally and theoretically in recent years[1, 2]. ILs consist exclusively of anions and ca- tions and do not contain any neutral molecule. They have many attractive properties, such as low vapor pressure, no… 相似文献
55.
The first molal hydrolysis quotient, Q1.1, of Mg2+ was measured potentiometrically from 1 to 250°C at ionic strengths of 0.11, 0.31, 1.01, and 5.0 mol-kg-1 in an aqueous NaCl medium using a hydrogen-electrode, concentration cell. Only hydrolysis of the first four percent of the
magnesium in solution could be followed before precipitation of brucite, Mg(OH)2(cr), occurred. The log Q1.1 values were fitted as a function of temperature and ionic strength using four adjustable parameters. The resulting constants
are compared with the limited existing low temperature data. At infinite dilution and 25°C the following quantities are reported:
logK
1.1 = -11.68±0.05, †Hso = 70.1±1.2 kJ-mol-1, †So = 11±4 J-K-1-mol-1, and †C
p
o
= 0 J-K-1-mor-1. At each ionic strength, including the values extrapolated to infinite dilution, the heat capacity change for the hydrolysis
reaction was zero,i.e., logQ
1.1 was found to be a linear function of the reciprocal temperature in Kelvin, at least over the measured range of l-250°C. The
hydrolysis constants at infinite dilution were modeled to 550°C and two kbar pressure with a function incorporating solvent
density using published results obtained at these extreme conditions. 相似文献
56.
The incorporation of explicit ions to mimic the effect of ionic strength or to neutralize the overall charge on a system in free energy calculations using molecular dynamics simulations is investigated. The difference in the free energy of hydration between two triosephosphate isomerase inhibitors calculated at five different ion concentrations is used as an example. We show that the free energy difference can be highly sensitive to the presence of explicit ions even in cases where the mutation itself does not involve a change in the overall charge. The effect is most significant if the molecule carries a net charge close to the site mutated. Furthermore, it is shown that the introduction of a small number of ions can lead to very severe sampling problems suggesting that in practical calculations convergence can best be achieved by incorporating either no counterions or by simulating at high ionic strength to ensure sufficient sampling of the ion distribution. 相似文献
57.
We report a molecular dynamics study of the solvation of UO2(2+), Eu3+ and Eu2+ ions in two "basic" (Lewis acidity) room-temperature ionic liquids (IL) composed of the 1-ethyl-3-methylimidazolium cation (EMI+) and a mixture of AlCl4- and Cl- anions, in which the Cl-/AlCl4- ratio is about 1 and 3, respectively. The study reveals the importance of the [UO2Cl4]2- species, which spontaneously form during most simulations, and that the first solvation shell of europium is filled with Cl- and AlCl4- ions embedded in a cationic EMI+ shell. The stability of the [UO2Cl4]2- and [Eu(III)Cl6]3- complexes is supported by quantum mechanical calculations, according to which the uranyl and europium cations intrinsically prefer Cl- to the AlCl4- ion. In the gas phase, however, [Eu(III)Cl6]3- and [Eu(II)Cl6]4- complexes are predicted to be metastable and to lose two to three Cl- ions. This contrasts with the results of simulations of complexes in ILs, in which the "solvation" of the europium complexes increases with the number of coordinated chlorides, leading to an equilibrium between different chloro species. The behavior of the hydrated [Eu(OH2)8]3+ complex is considered in the basic liquids; the complex exchanges H2O molecules with Cl- ions to form mixed [EuCl3(OH2)4] and [EuCl4(OH2)3]- complexes. The results of the simulations allow us to better understand the microscopic nature and solvation of lanthanide and actinide complexes in "basic" ionic liquids. 相似文献
58.
Fonseca GS Umpierre AP Fichtner PF Teixeira SR Dupont J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3263-3269
Stable transition-metal nanoparticles of the type [M(0)](n) are easily accessible through the reduction of Ir(I) or Rh(III) compounds dissolved in "dry" 1-n-butyl-3-methylimidazolium hexafluorophosphate ionic liquid by molecular hydrogen. The formation of these [M(0)](n) nanoparticles is straightforward; they are prepared in dry ionic liquid whereas the presence of the water causes the partial decomposition of ionic liquid with the formation of phosphates, HF and transition-metal fluorides. Transmission electron microscopy (TEM) observations and X-ray diffraction analysis (XRD) show the formation of [Ir(0)](n) and [Rh(0)](n) nanoparticles with 2.0-2.5 nm in diameter. The isolated [M(0)](n) nanoparticles can be redispersed in the ionic liquid, in acetone or used in solventless conditions for the liquid-liquid biphasic, homogeneous or heterogeneous hydrogenation of arenes under mild reaction conditions (75 degrees C and 4 atm). The recovered iridium nanoparticles can be reused several times without any significant loss in catalytic activity. Unprecedented total turnover numbers (TTO) of 3509 in 32 h, for arene hydrogenation by nanoparticles catalysts, have been achieved in the reduction of benzene by the [Ir(0)](n) in solventless conditions. Contrarily, the recovered Rh(0) nanoparticles show significant agglomeration into large particles with a loss of catalytic activity. The hydrogenation of arenes containing functional groups, such as anisole, by the [Ir(0)](n) nanoparticles occurs with concomitant hydrogenolysis of the C-O bond, suggesting that these nanoparticles behave as "heterogeneous catalysts" rather than "homogeneous catalysts". 相似文献
59.
60.