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以从塔板理论得到的色谱流出曲线为基础,推导了高效液相色谱(HPLC)双流动相分离场中实现峰压缩时,峰压缩因子(峰压缩后的半峰宽与未进行峰压缩时的半峰宽的比值)和峰高表示的灵敏度变化(峰压缩后的峰高与未进行峰压缩时的峰高的比值)的关系,结果表明峰高表示的灵敏度增加值等于峰压缩因子的倒数.并用色氨酸、香豆素、苯和2-硝基酚在不同速率差实现堆积时的相关参数进行了验证.实验结果表明,这些化合物在各个峰压缩条件下的峰压缩因子倒数和实际灵敏度增加值相等,实验结果与理论推导结果一致.考察了该关系式在实际样品测定中的应用,结果表明灵敏度增加值等于峰压缩因子的倒数,这也与理论部分的结果一致. 相似文献
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将方阱势能函数视为硬球势和一个短程均匀负势的叠加,并由统计力学方法导出了相应的状态方程,这个方程包含两个定标的径向分布函数.利用已知的压缩因子分子动力学模拟数据,回归得到了这两个径向分布函数,从而建立了一个新的方阱流体状态方程.它的吸引项要比Alder等人回归得到的简单得多,与方阱流体压缩因子的MD数据一致性也更好,特别是在高密度区域. 相似文献
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构建了一种新的拓扑指数ND,可对分子结构实现惟一性表征,具有优良的结构选择性.用ND指数对烷烃的偏心因子ω和临界压缩因子ZC进行研究,结果表明烷烃的偏心因子ω和临界压缩因子ZC可用下述二式来定量描述:ln(2.336 5ω)=0.008 288ND1 0.001 857ND2 0.000 551ND3 0.855 206;ln(ZC0.185)=0.021 496ND1 0.004 385ND2 0.001 235ND32.135 614,用上述二式分别对烷烃的偏心因子和临界压缩因子进行计算,计算值与实验值吻合良好. 相似文献
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本采用压缩X因子导数光谱技术实现了宽峰体系灵敏度的大幅度提高,提出了测定痕量锗的方法。在0.72mol/LH2SO4和3.0mol/LH3PO4的混酸介质中,锗-水杨基荧光酮-OP三元显色体系的压缩X因子四阶导数光谱摩尔响应系数达1.89×10^6L.mol^-1.cm^-1,灵敏度比常规光度法高12.4倍;最低检测出限为0.00033mg/L,比常规光谱法低4倍;选择性也进一步提高,绝大多数离 相似文献
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根据对应状态定律,Hougen和Watson应用实验数据计算许多气体的压缩因子z,并将其平均值表示成对比参数(T_r,p_r)的函数,这样就建立了普遍化压缩因子图。只要稍加注意,不难发现,此图有一个显著的特点,各种不同的等T_r,曲线相交于两点:一点当p_r→0时, 相似文献
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介绍了自行设计的测量“弯曲-压缩”位移量的仪器与材料试验机的联要应用,该系统可测得精确的位移量,并可自动绘图,开发了原仪器设备的功能,提高了它的利用率和效率。 相似文献
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不同品种环保橡胶填充油对乳聚丁苯橡胶性能影响研究 总被引:1,自引:0,他引:1
通过使用差示扫描量热仪(DSC)、橡胶加工分析仪(RPA)和动态压缩生热仪测试,分别研究了采用国内外不同品种的环保型橡胶填充油所制备的乳聚丁苯橡胶的热性能、动态力学性能以及动态压缩生热性能,并与非环保型丁苯橡胶SBR1712及环保型丁苯橡胶SBR1723进行了对比。结果表明,采用环保型芳烃油(TDAE)所制备的乳聚丁苯橡胶损耗因子最大,生热稍高于其它品种环保油;采用克拉玛依石化环保型环烷油(AP-10)所制备的乳聚丁苯橡胶动态压缩生热性能最好。 相似文献
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Cavalcanti LP Tho I Konovalov O Fossheim S Brandl M 《Colloids and surfaces. B, Biointerfaces》2011,85(2):1107-160
The mechanical properties of liposome membranes are strongly dependent on type and ratio of lipid compounds, which can have important role in drug targeting and release processes when liposome is used as drug carrier. In this work we have used Brewster's angle microscopy to monitor the lateral compression process of lipid monolayers containing as helper lipids either distearoyl phosphatidylethanolamine (DSPE) or dioleoyl phophatidylethanolamine (DOPE) molecules on the Langmuir trough. The compressibility coefficient was determined for lipid blend monolayers containing the helper lipids above, cholesterol, distearoyl phosphatidylcholine (DSPC) and pegylated-DSPE at room temperature. Two variables, the cholesterol fraction and the ratio ρ between the helper lipid (either DSPE or DOPE) and the reference lipid DSPC, were studied by multivariate analysis to evaluate their impact on the compressibility coefficient of the monolayers. The cholesterol level was found to be the most significant variable for DSPE blends while the ratio ρ was the most significant one for DOPE blend monolayers. It was also found that these two variables can exhibit positive interaction and the same compressibility value can be obtained with different blend compositions. 相似文献
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Hans-Gerd Janssen Henri Snijders Carel Cramers Peter Schoenmakers 《Journal of separation science》1992,15(7):458-466
The influence of the pressure drop on the efficiency and speed of analysis in packed and open tubular supercritical fluid chromatography (SFC) is described: methods previously developed to describe the effects of mobile phase compressibility on the performance of open tubular columns in SFC have been extended to packed columns. The Horvath and Lin equation has been used to elucidate the influence of variations in velocity, diffusivity, and capacity factor along the column on the overall efficiency of packed column SFC. In packed columns, in contrast with the situation in open tubular columns, because the increase in velocity is no longer compensated by an increase in diffusion coefficients, the increase in both linear velocity and capacity factor which result from a significant pressure drop cause the plate height to increase along the column. The effect of fluid decompression along the length of the column on the speed of analysis in SFC has been studied and numerical expressions derived which enable calculation of compressibility correction factors for the plate height. Both the f1 and f2 correction factors remain very close to unity for acceptable pressure drops, which means that the pressure drop has virtually no effect on the number of plates generated per unit time for an unretained component. For retained species, the decompression of the mobile phase across the column causes the capacity factor to increase and hence leads to increased analysis times. 相似文献
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张秉坚 《高等学校化学学报》1995,16(9):1440-1444
提出在Barker与Henderson的压缩性近似推导中,相邻壳层之间的分子数应该相关,导出了相关系数和改进的二级微扰项,提高了高级微扰项在较高密度区的准确性。对二级以上的高级微扰项采用Barker与Henderson的近似方法,得到一个简单的微扰理论表达式,以硬球势为参考势,方阱势为微扰势,用一新的级数形式的径向分布函数导出了自由能、内能、比热、压缩因子的级数表达式。其四项截断式的计算结果与MC、MD计算机模拟值符合较好。 相似文献
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L.A. Utracki 《European Polymer Journal》2009,45(7):1891-1380
Clay-containing polymeric nanocomposites (CPNC) with polystyrene (PS) or polyamide-6 (PA-6) matrix were studied within T = 300-600 K and P = 0.1-190 MPa. From the Pressure-Volume-Temperature (PVT) data the derivatives: compressibility, κ, and thermal expansion coefficient, α, were computed as functions of T, P and clay content, w. Dependence of these coefficients on P and T were significantly different for the amorphous PS than for the semi-crystalline PA-6. In the PS plots of κ and αvs.T the presence of secondary transitions, Tβ/Tg ≈ 0.9 ± 0.1 and Tc/Tg = 1.2 ± 0.1, were detected and the clay effect at low T was prominent, affecting the physical aging. The isobaric values of α = α(T) were characterized by nearly T-independent values in the glassy and molten phase, connected by a large transitory region stretching from the ambient pressure values of Tg to Tc; this region was even more prominent in κ = κ(T). The derivative properties of PA-6 based CPNC were distinctly different. Here, the isobaric κ = κ(T) followed the same dependence on both sides of the melting zone, while the isobaric α = α(T) dependencies were dramatically different for the solid and molten phase; at T < Tmα linearly increased with T, after melting its value sharply decreased, and then at T > Tm (depending on w and P) either increased or decreased with T. Interpretation of the behavior in the melt and glass is based on the Simha-Somcynsky (S-S) cell-hole theory while that of the semicrystalline state on the Midha-Nanda-Simha-Jain (MNSJ) cell theory. In spite of the nonequilibrium conditions below the main transition point, Tg or Tm, the theories well predict the observed dependencies. 相似文献
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《Physics and Chemistry of Liquids》2012,50(2):135-142
Abstract Viscosity and isothermal compressibility of a simple liquid have been related by means of a closed-form equation for the low-shear viscosity of a liquid dispersion of solid particles. It involves macroscopic density, total correlation function and free volume. The equation achieved, which does not have an explicit solution, was approximated and applied to two sets of experimental data, where the free volume contribution was evaluated on the basis of experimental values of either volumes at zero fluidity or force constants for second virial coefficients and pair interaction potentials. 相似文献
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The evolution of the unit-cell parameters of CaZrO3 perovskite, an orthorhombic perovskite belonging to space group Pbnm, have been determined to a pressure of 8.7 GPa at room temperature using single-crystal X-ray diffraction measurements. A fit of a third-order Birch-Murnaghan equation of state to the pressure-volume data yields values of V0=258.04(2) Å3, KT0=154(1) GPa and K0′=5.9(3). Although CaZrO3 perovskite does not exhibit any phase transitions in this pressure range, the compression of the structure is anisotropic with [010] approximately 20% less compressible than either [100] or [001]. Compressional moduli for the unit cell parameters are: Ka0=142(1) GPa and Ka0′=4.4(2), Kb0=177(2) GPa and Kb0′=9.4(5), Kc0=146(2) GPa and Kc0′=5.4(4). Comparison with other orthorhombic Ca-oxide perovskites shows that there is systematic increase in compressional anisotropy with increasing distortion from cubic symmetry. 相似文献
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R. N. Haward 《Journal of Polymer Science.Polymer Physics》1969,7(1):219-229
The compressibility of polyisobutylene and polystyrene above their glass transition temperature is treated as the sum of two parts; a free-volume compressibility and, as originally suggested by Bridgman, a compressibility of the molecules themselves. Two different models are used to treat the free-volume compressibility, and as a result values for the molecular compressibility are estimated. These are in reasonable agreement with other values in the literature. The magnitude of this “molecular compressibility” is then considered in relation to some existing treatments of intermolecular forces. These suggest that intermolecular contacts are more compressible than covalent bonds, and on this basis the observed levels of molecular compressibility can be explained. 相似文献
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Dr. Andrey Yu. Manakov Dr. Anna Yu. Likhacheva Dr. Vladimir A. Potemkin Dr. Andrey G. Ogienko Dr. Alexander V. Kurnosov Dr. Aleksei I. Ancharov 《Chemphyschem》2011,12(13):2476-2484
Experimental data on the pressure dependence of unit cell parameters for the gas hydrates of ethane (cubic structure I, pressure range 0–2 GPa), xenon (cubic structure I, pressure range 0–1.5 GPa) and the double hydrate of tetrahydrofuran+xenon (cubic structure II, pressure range 0–3 GPa) are presented. Approximation of the data using the cubic Birch–Murnaghan equation, P=1.5B0[(V0/V)7/3?(V0/V)5/3], gave the following results: for ethane hydrate V0=1781 Å3, B0=11.2 GPa; for xenon hydrate V0=1726 Å3, B0=9.3 GPa; for the double hydrate of tetrahydrofuran+xenon V0=5323 Å3, B0=8.8 GPa. In the last case, the approximation was performed within the pressure range 0–1.5 GPa; it is impossible to describe the results within a broader pressure range using the cubic Birch–Murnaghan equation. At the maximum pressure of the existence of the double hydrate of tetrahydrofuran+xenon (3.1 GPa), the unit cell volume was 86 % of the unit cell volume at zero pressure. Analysis of the experimental data obtained by us and data available from the literature showed that 1) the bulk modulus of gas hydrates with classical polyhedral structures, in most cases, are close to each other and 2) the bulk modulus is mainly determined by the elasticity of the hydrogen‐bonded water framework. Variable filling of the cavities with guest molecules also has a substantial effect on the bulk modulus. On the basis of the obtained results, we concluded that the bulk modulus of gas hydrates with classical polyhedral structures and existing at pressures up to 1.5 GPa was equal to (9±2) GPa. In cases when data on the equations of state for the hydrates were unavailable, the indicated values may be recommended as the most probable ones. 相似文献
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Alireza Bahadori Saeid Mokhatab Brian F. Towlera 《天然气化学杂志》2007,16(4):349-353
Natural gases containing sour components exhibit different gas compressibility factor(Z) behavior than do sweet gases.Therefore,a new accurate method should be developed to account for these differences.Several methods are available today for calculating the Z-factor from an cquation of state. However,these equations are more complex than the foregoing correlations,involving a large number of parameters,which require more complicated and longer computations.The aim of this study is to develop a simplified calculation method for a rapid estimating Z-factor for sour natural gases containing as much as 90% total acid gas.In this article,two new correlations are first presented for calculating the pseudo- critical pressure and temperature of the gas mixture as a function of the gas specific gravity.Then,a simple correlation on the basis of the standard gas compressibility factor chart is introduced for a quick estimation of sweet gases' compressibility factor as a function of reduced pressure and temperature.Finally,a new corrective term related to the mole fractions of carbon dioxide and hydrogen sulfide is developed. 相似文献