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201.
Rabindra N. Roy Jill Cramer Victoria Randon Demara Willard Jennifer L. Walter William S. Good Amanda Kilker Lakshmi N. Roy 《Journal of solution chemistry》1998,27(5):425-434
The second acidic dissociation constants pK
2 of the ampholyte N-(2-hydroxyethyl) piperazine-N-2-hydroxypropanesulfonic acid (HEPPSO) have been determined at seven temperatures from 5 to 55°C from emf measurements utilizing hydrogen and silver–silver chloride cells without liquid junction. The thermodynamic quantities, G°, H°,S°, and C
p
o
have been calculated from the temperature coefficient of pK
2. At 25°C, the pK
2 = 8.042 and at 37°C, pK
2 = 7.876; hence, buffer solutions of HEPPSO and NaHEPPSOate are important for pH control in the region close to that of clinical fluids (blood serum). Conventional pH values from 5 to 55°C as well as those obtained from liquid junction correction at 25 and 37°C have been reported for three buffer solutions with the compositions (molality scale): (1) equimolal mixture of HEPPSO (0.04 m) + NaHEPPSOate (0.04 m) + NaCl (0.12 m); (2) HEPPSO (0.08 m) + NaHEPPSOate (0.08 m); and (3) HEPPSO (0.08 m) + NaHEPPSOate (0.08 m) + NaCl (0.08 m). 相似文献
202.
S. N. Kreitmeier G. L. Liang D. W. Noid B. G. Sumpter 《Journal of Thermal Analysis and Calorimetry》1996,46(3-4):853-869
Thermal analysis by classical molecular dynamics simulations is discussed on hand of heat capacity of crystals of 9600 atoms. The differences between quantum mechanical and classical mechanical calculations are shown. Anharmonicity is proven to be an important factor. Finally, it is found that defects contribute to an increase in heat capacity before melting. The energy of conformational gauche defects within the crystal is only about 10% due to internal rotation. The other energy must be generated by cooperative strain. The conclusion is that the next generation of faster computers may permit wider use of molecular dynamics simulations in support of the interpretation of thermal analysis.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthday 相似文献
203.
204.
《中国化学》2017,35(7):1091-1097
In this work, a new porous Zr‐based metal‐organic framework (MOF ) with a large Brunner‐Emmet‐Teller (BET ) surface area was prepared by the solvothermal method using 4,4’‐(naphthalene‐1,4‐diyl)dibenzoic acid (NDDA ) as the organic ligand, and the luminescent detection performance was studied systematically. The experiments combing with computations indicate that the as‐synthesized material can sensitively and selectively detect nitro explosives and metal ions, especially for 2,4,6‐trinitrophenol (TNP ) and Fe3+, due to the possible electron transfer from inorganic moieties to organic moieties with naphthalene part. Interestingly, owing to its high porosity and large surface area, this Zr‐MOF showed quick luminescent response time (in 1 min) for TNP and Fe3+. The results obtained may provide useful information for the design of MOFs with the large permanent porosity in sensing applications for large molecules in the future. 相似文献
205.
合成了两种固态稀土丙氨酸配合物[Ho2(Ala)4(H2O)8]Cl6和[ErY(Ala)4(H2O)8](ClO4)6 (Ala为丙氨酸),用量热和热分析方法研究了这两种配合物的热力学性质.用全自动高精密绝热量热计测定了在78~377 K温区内的低温热容.对于[Ho2(Ala)4(H2O)8]Cl6,在214~255 K温区内发现一固-固相变,其相变温度为235.09 K.对于[ErY(Ala)4(H2O)8](ClO4)6,在99~121 K温区内也发现一固-固相变,其相变温度为115.78 K. [Ho2(Ala)4(H2O)8]Cl6固-固相变焓为3.02 kJ• mol-1,相变熵为12.83 J•K-1•mol-1; [ErY(Ala)4(H2O)8](ClO4)6 固-固相变焓为1.96 kJ•mol-1,相变熵为16.90 J•K-1•mol-1.同时,用TG技术在40~800 ℃温区研究了两配合物的热稳定性.由TG/DTG曲线分析可知, [Ho2(Ala)4(H2O)8]Cl6从80 ℃到479 ℃热分解分两步完成, [ErY(Ala)4(H2O)8](ClO4)6从120 ℃到430 ℃热分解分三步完成. 相似文献
206.
V. P. Korolev 《Journal of Structural Chemistry》2006,47(6):1084-1090
A new equation is suggested to define the temperature dependence of the Gibbs energy of hydration of hydrophobic substances: ΔG 0 = b 0 + b 1 T + b 2lnT. According to this equation, the hydration heat capacity is in inverse proportion to temperature. Consistent values of hydration heat capacity of nonpolar solutes have been obtained for different temperatures using data on solubility and dissolution enthalpy. The contributions of the hydrocarbon radicals and OH group to the heat capacity of hydration of the compounds were found for the temperature range 248–373 K. The hydration heat capacity of the hydroxyl group has a weak dependence on temperature and increases by only 12 J/(mol·K) in the specified temperature interval. Changes in the hydration entropy of hydrophobic and OH groups are calculated for the temperature increasing from 248 K to 373 K. 相似文献
207.
T. Ishikawa S. Yamashita Y. Nakazawa A. Kawamoto M. Oguni 《Journal of Thermal Analysis and Calorimetry》2008,92(2):435-438
Thermodynamic investigation of an organic superconductor κ-(BEDT-TTF)2Ag(CN)2H2O in which the BEDT-TTF dimers are arranged in the κ-type structure in the donor layers is performed by the relaxation calorimetric
technique at low temperatures and under magnetic fields. A thermal anomaly related to the superconductive phase transition
was observed at 5 K. The existence of residual γ* in the superconductive state is about 18% of the normal state γ value, which is larger than those of κ-(BEDT-TTF)2Cu(NCS)2, and κ-(BEDT-TTF)2Cu[N(CN)2]Br salt. The lattice heat capacity reflected on the β-term in the low-temperature heat capacity was found to be affected
by the cooling rate. The disorder produced in the network structure constructed by hydrogen bond in the insulating layer is
considered to give low-energy phonon excitations reflected in the heat capacity. 相似文献
208.
本文用精密自动绝热量热仪测定了2-甲基-2-丁醇在80~305 K温区的热容,从热容曲线(Cp-T) 发现三个固-固相变和一个固-液相变, 其相变温度分别为T = 146.355, 149.929, 214.395, 262.706 K。从实验热容数据用最小二乘法得到以下四个温区的热容拟合方程。在80~140K温区, Cp,m = 39.208 + 8.0724X - 1.9583X2 + 10.06X3 + 1.799X4 - 7.2778X5 + 1.4919X6, 折合温度X = (T –110) / 30; 在 155 ~ 210 K温区, Cp,m = 70.701 + 10.631X + 12.767X2 + 0.3583X3 - 22.272X4 - 0.417X5 + 12.055X6, X = (T –182.5) /27.5; 在220 ~ 250 K温区, Cp,m = 99.176 + 7.7199X - 26.138X2 + 28.949X3 + 0.7599X4 - 25.823X5 + 21.131X6, X = (T – 235)/15; 在 270~305 K温区, Cp,m =121.73 + 16.53 X- 1.0732X2 - 34.937X3 - 19.865X4 + 24.324X5 + 18.544X6, X = (T –287.5)/17.5。从实验热容计算出相变焓分别为0.9392, 1.541, 0.6646, 2.239 kJ×mol-1; 相变熵分别为6.417, 10.28, 3.100, 8.527 J×K-1×mol-1。根据热力学函数关系式计算出80~305 K温区每隔5 K的热力学函数值 [HT –H298.15]和 [ST –S298.15]。 相似文献
209.
应用以氢氧化物共沉淀为前驱体的高温固相烧结法合成LiNi1/3Mn1/3Co1/3O2正极材料,研究了沉淀温度及烧结过程锂盐投入量对该材料的结构和电化学性能的影响.结果表明,以室温(-20℃)下合成的氢氧化物为前驱体制备的LiNi1/3Mn1/3Co1/3O2具有较好的电化学性能.高温固相烧结会导致部分LiOH损失,因而在合成过程中需加入过量的氢氧化锂,实验表明Li1.08Ni1/3Mn1/3Co1/3O2材料的电化学性能最优. 相似文献
210.