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101.
For any particular fluid, the set of three critical constants (CC) – pressure Pc, temperature Tc and molar volume Vc – has a central importance in defining the physical behaviour of the fluid in the gas and liquid states. However, little attention seems to have been paid in the past to the relations between the CC of different substances. In the present paper, some simple and apparently novel relations have been found between the three CC for the set of four noble gases: Ne, Ar, Kr, Xe. Defining the critical quotient Qc ≡ RTc/Pc (where R is the Gas Constant) the correlations may be summarised by the dual equation: (Vc/cm3 mol−1) = 27 + 0.31 (Tc/K) = 3.3 + 0.280 (Qc/cm3 mol−1), which describes the CC data for the quartet Ne–Xe with an average uncertainty of 0.5%. Regarding the other two noble gases, the two isotopes of the lightest member, 3He and 4He, show the deviations from these relations that are expected from quantal effects and their low molar masses; while for the heaviest member, Rn, the correlations enable a value of 145(5) cm3 mol−1 to be estimated for Vc that is not otherwise well defined in the literature. By contrast, and contrary to the general assumption, the second lightest member, Ne, apparently does not show appreciable quantal effects in the area, so that Ne–Xe may be considered together as a group. These correlations are compared with the behaviour of a selection of polyatomic fluids; in these comparisons, the NG dual correlation equation provides a reference line defining the presumed simplest behaviour. This and related areas show a “Residual Volume Effect”, in that extrapolating the equivalent temperature and energy parameters to zero for the state of zero-mass point particles, referred to here as the hypothetical element zeronium (Ze), the system in each case still has a finite intercept; this intercept amounts to essentially 34% of the average volume for the present quartet Ne–Xe, rather than the zero volume expected for this condition. 相似文献
102.
Eylem Turan Serkan Demirci Tuncer Caykara 《Journal of Polymer Science.Polymer Physics》2008,46(16):1713-1724
Dual temperature‐ and pH‐sensitive hydrogels composed of N‐isopropylacrylamide (NIPAM) and 2‐acrylamido‐2‐methyl‐propanosulfonic acid (AMPS) were prepared by free‐radical crosslinking copolymerization in aqueous solution at 22 °C. The mole percent of AMPS in the comonomer feed was varied between 0.0 and 7.5, while the crosslinker ratio was fixed at 5.0/100. The effect of AMPS content on thermo‐ and pH‐ induced phase transitions as well as equilibrium swelling/deswelling, interior morphology and network structure was investigated. The volume phase transition temperature (VPT‐T) was determined by both swelling/deswelling measurements and differential scanning calorimetry (DSC) technique. In addition, the volume phase transition pH (VPT‐pH) was detected from the derivative of the curves of the swelling ratio (dQv/dpH) versus pH. The polymer‐solvent interaction parameter (χ) and the average molecular mass between crosslinks ( ) of hydrogels were calculated from swelling ratios in buffer solutions at various pHs. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter of hydrogels were also determined by using the modified Flory–Rehner equation. The negative values for ΔH and ΔS indicated that the hydrogels had a negative temperature‐sensitive property in water, that is, swelling at a lower temperature and shrinking at a higher temperature. It was observed that the experimental swelling data of hydrogels at different temperature agreed with the modified Flory‐Rehner approach based on the affine network model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1713–1724, 2008 相似文献
103.
H2CO和NO2反应机理的密度泛函理论计算研究 总被引:2,自引:2,他引:2
用密度泛函理论方法在UB3LYP/ 6-311++G(d,p)并包含零点能水平上计算得到了H2CO和NO2反应的势能面.在势能面上找到了由H2CO和NO2反应生成HCO和trans-HONO的两条反应通道.直接H迁移反应通道的势垒只有90.54 kJ*mol-1,是主要的反应通道,其TST速率是7.9 cm3*mol-1*s-1,与文献值相符;另一条通道是H2CO异构化为trans-HCOH,然后C位H迁移,最后生成的HOC分子异构化为HCO,这条通道反应势垒高达348.03 kJ*mol-1,是一条次要反应通道. 相似文献
104.
NiO/γ-Al2O3催化剂中NiO与γ-Al2O3间的相互作用 总被引:27,自引:0,他引:27
利用溶胶-凝胶法制备了不同含量的 NiO/γ-Al_2O_3催化剂,通过XRD,XPS和 TPR等技术考察了制备方法、NiO含量和焙烧温度对催化剂结构和Ni存在状态的影响,发现溶胶-凝胶法制备的催化剂活性组分NiO与担体γ-Al_2O_3间具有强相互作用.详细地讨论了Ni物种的还原状态与以“Ni~0”为活性中心的催化反应的活性之间的关系.溶胶-凝胶法制备的催化剂经高温焙烧后,Ni以一种类尖晶石结构的固溶体形式存在,这种固溶体态尖晶石可能会抑制Ni的烧结和流失,提高催化剂的稳定性. 相似文献
105.
选取四种不同种类离子液体(ILs),1-丁基-3-甲基咪唑溴化物([Bmim]Br)、1-丁基-3-甲基咪唑四氟硼酸盐([Bmim]BF_4)、1-丁基-3-甲基咪唑硫酸氢盐([Bmim]HSO_4)、1-丁基-3-甲基咪唑磷酸二氢盐([Bmim]H_2PO_4)与30%H_2O_2溶液在温和条件下对两种高硫脱灰煤样(LS、QX)进行脱硫实验研究。用化学法测定脱硫前后煤样形态硫含量,并利用傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)及热重(TG)对脱硫前后的煤样进行表征。结果表明,离子液体的加入使H_2O_2氧化脱硫能力增强,煤中硫铁矿硫和有机硫化物硫被显著脱除;经ILs/H_2O_2体系作用后的煤样中小粒径的颗粒减少,颗粒间的缝隙增大,煤表面的凹坑明显,热重实验结果表明,ILs/H_2O_2体系作用后的煤样相对于原煤热失重增大,部分挥发性物质释放峰温提前。 相似文献
106.
107.
I.IntroductionInordertostudybifurcationsofnonlineardynamicalsystemsinthedegeneratecasesofhighercodimensionnumber(>3),wemustcomputenormalformsofhigherorderfornonlineardynamicalsystems.Inrecenttwentyyearsmanyscientistsmadeveryimportantcontributionstodevelop… 相似文献
108.
研究含双周期分布的圆形刚性夹杂在无穷远受纵向剪切的弹性平面问题,遵循复合材料中各夹杂相互影响的重要条件。采用复变函数方法。构造相应模型的复应力函数。通过坐标变换,同时满足夹杂边界位移条件,再利用围线积分将求争方程组化为线性代数方程组。导出了圆形刚性夹杂双周期分布的界面应力解析表达式。算例给出了界面应力最大值与夹杂间距的变化规律。求出了刚性夹杂的合理间距问题,本文发展的分析方法为研究夹杂材料的细观机理探索了一条有效的分析途径。 相似文献
109.
In the present paper, the effective elastic moduli of an inhomogeneous medium with cracks are derived and obtained by taking
into account its microstructural properties which involve the shape, size and distribution of cracks and the interaction between
cracks. Numerical results for the periodic microstructure of different dimensions are presented. From the results obtained,
it can be found that the distribution of cracks has a significant effect on the effective elastic moduli of the material.
The project supported by the National Education Committee for Doctor 相似文献
110.
时域边界元法分析撞水响应 总被引:6,自引:1,他引:6
基于势流理论,考虑流场的可压缩性,首先利用积分变换导得了势流问题的一个动力学倒易定理,在此基础上,进而求得问题对应的时空边界积分方程,然后通过对边界和时间轴同时离散,建立了一组有递推形式的时间边界元方程最后结合液面条件和物体运动方程耦全求解得到了刚体的撞水响应。 相似文献