Hygrometric Determination of Water Activities and Osmotic and Activity Coefficients of NH4Cl–LiCl–H2O at 25°C

The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg^{– 1} for different ionic-strength fractions y of NH₄Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions.     

线性唯象传热定律下光驱动发动机的最优路径

以存在热漏、摩擦等不可逆性,以双分子反应系统2SO3FS2O6F2为工质的光驱动发动机为研究对象,考虑工质与环境之间传热服从线性唯象传热定律[q∝Δ(T-1)],分别以输出功最大和熵产生最小为目标对整个循环活塞运动的最优路径进行研究.利用最优控制理论得出了活塞运动路径及工质温度的最优构型,给出了最优构型的数值算例,并与牛顿传热定律[q∝Δ(T)]下的最优构型进行了比较.     

Studies on external peak broadening in open-tubular liquid chromatography systems using the exponentially modified Gaussian model

Summary To optimize performance in Open-Tubular Liquid Chromatography (OTLC) it is necessary to minimize external peak broadening. To see how to reduce the external broadening an insight into its origins is required. This can be obtained by careful evaluation of experimental results with peak deconvolution methods based on the exponentially modified Gaussian model and comparison with theoretical predictions. It is assumed that the column response is Gaussian and that the responses due to the external effects are exponential.For peak deconvolution the algorithm described by Yau was used. Simulations were carried out to check the performance of the algorithm in calculating the standard deviation and the time constant. The effects of the presence of more than one time constant and of the number of data points and their position were investigated. The limits within which reliable results can be obtained are reported.Experimental results were obtained with laser-induced fluorescence and mass spectrometric detection. It is shown that the Yau algorithm can be used to obtain physically realistic estimates of the contribution to peak distortion in the various system components. By suitable design external effects can be reduced to the order of 1 nl and in some cases even lower limits can be reached.Part of this paper was presented at the 3rd Workshop on LC/MS and MS/MS, October, 24–26, 1984 in Montreux, Switzerland.     

The statistical overlap theory of chromatography using power law (fractal) statistics

The chromatographic dimensionality was recently proposed as a measure of retention time spacing based on a power law (fractal) distribution. Using this model, a statistical overlap theory (SOT) for chromatographic peaks is developed that estimates the number of peak maxima as a function of the chromatographic dimension, saturation and scale. Power law models exhibit a threshold region whereby below a critical saturation value no loss of peak maxima due to peak fusion occurs as saturation increases. At moderate saturation, behavior is similar to the random (Poisson) peak model. At still higher saturation, the power law model shows loss of peaks nearly independent of the scale and dimension of the model. The physicochemical meaning of the power law scale parameter is discussed and shown to be equal to the Boltzmann-weighted free energy of transfer over the scale limits. The scale is discussed. Small scale range (small β) is shown to generate more uniform chromatograms. Large scale range chromatograms (large β) are shown to give occasional large excursions of retention times; this is a property of power laws where "wild" behavior is noted to occasionally occur. Both cases are shown to be useful depending on the chromatographic saturation. A scale-invariant model of the SOT shows very simple relationships between the fraction of peak maxima and the saturation, peak width and number of theoretical plates. These equations provide much insight into separations which follow power law statistics.     

费托反应本征动力学中合成气分压对反应速率的影响

利用高通量动力学反应器测量了本征条件下钴基费托催化剂上反应物消耗速率rCO和产物生成速率rCH4随固定床床层的分布,并考察了它们在不同入口分压(p0CO,p0H2)条件下的变化.结果表明,入口氢碳比(H/C)0=p0H2/p0CO为影响速率的敏感外部变量,反应速率随(H/C)0的增加而加快;而合成气总压p0H2+CO则...     

Gauss光束通过单丝的Fresnel衍射

本文用数值计算方法研究了Ｇａｕｓｓ光束照射下的Ｆｒｅｓｎｅｌ衍射，尤其是单丝的衍射，导出主极大区有明显的三分裂特征，并将求得结果与已有平面波照射下的Ｆｒｅｓｎｅｌ单缝衍射进行对比，在相当宽的范围内，实验证实了我们的理论结果。     

The minimum heat consumption for heat-driven binary separation processes with linear phenomenological heat transfer law

The optimal performance of heat-driven binary separation processes with linear phenomenological heat transfer law(q∝△(T-1)) is analyzed by taking the processes as heat engines which work between high-and low-temperature reservoirs and produce enthalpy and energy flows out of the system,and the temperatures of the heat reservoirs are assumed to be time-and space-variables.A numerical method is employed to solve convex optimization problem and Lagrangian function is employed to solve the average optimal contr...     

Partial molar isentropic compressibilities and volumes of selected electrolytes and nonelectrolytes in dimethylsulfoxide

Precision densities and sound velocities for solutions of selected univalent electrolytes and nonelectrolytes in DMSO have been measured at 25°C, and apparent molar isentropic compressibilities and volumes evaluated. The data were extrapolated to infinite dilution to obtain standard state partial molar quantities, K _s,2 ^° , and V ₂ ^° . Values of V ₂ ^° and K _s,2 ^° for alkali metal halides in DMSO are very similar to those in water. The results confirm conclusions derived from data in water and other nonaqueous solvents that K _s,2 ^° and V ₂ ^° for alkali metal halides are strongly dependent on solvent compressibility. K _s,2 ^° becomes more negative and V ₂ ^° decreases as solvent compressibility increases. Attempts to determine ionic K _s,2 ^° values suggest that a significant dissymmetry exists between ₄P⁺ and ₄B^– in DMSO, whereas in water and MeOH, these large ions appear to behave similarly. Ionic V ₂ ^° values support this conclusion. Steric hindrance in the DMSO molecule is believed to be responsible for this dissymmetry.