级联二阶非线性法布里-珀罗谐振腔特性分析

在小信号近似下,得出了级联二阶过程的表达式。利用该式的有效三阶极化率的表达式,讨论了存在二阶非线性光学晶体的法－珀谐振腔的非线性光学特性。分析表明,由于谐振腔的存在,通过非线性晶体的功率密度超过入射功率密度几十倍以上,因而产生较大的、随相位失配变化的非线性相位漂移。当相位失配接近２π时,获得基叔光的最大相位漂移。该最大相位漂移对应的相位失配随着入射功率密度、非线性晶体的地阶极化率和晶体长度而变化。     

Transfer activity coefficient of the proton in water-pyridine mixtures. A comparison of some extrathermodynamic assumptions

Various water-pyridine mixtures have been selected in order to compare several of the most popular extrathermodynamic assumptions involved in the determination of the transfer activity coefficient of the proton, _t(H⁺). Two techniques have been utilized for this purpose: voltammetry [study of the ferrocene, ferricyanide, or thallium(1) systems] and potentiometry at equilibrium (emf measurements of various galvanic cells, including liquid junctions and hydrogen electrode or silver electrode as a test electrode). The assumptions have been classified into various groups [e.g., _t(Z^p+)=_t(Z^q+) or _t(X^–)=_t(Y⁺)], and the values of _t(H⁺) have been experimentally determined in each case. The results vary depending upon the basic assumption (several pH units); less important differences (e.g., 0.5 pH unit) occur within a given group, and this may be assigned to the nature of the reference species chosen. A simple model of solvation has been also examined; the application of the law of mass action to the corresponding equilibrium provides results close to the _t(X^–) =_t(Y⁺)type of assumptions which ultimately leads to most self-consistent results.     

Dissociation constants of the ampholyte glycine in 50 mass % methanol-water from 5 to 55°C,with related thermodynamic quantities

The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K ₁)for the process HG⁺H⁺+G^± is expressed as a function ofT(^oK) by the equation pK ₁ = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK ₁is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole^–1, G°=4038 cal-mole^–1, S°=–8.52 cal-°K^–1-mole^–1, and C _p ^o =–53 cal-°K^–1-mole^–1. The second acidic dissociation constant (K ₂)for the process G^±H⁺+G^– over the temperature range studied is given by the equation pK ₂ = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK ₂is 9.578 in MeOH–H₂O as compared with 9.780 in water, whereas H° is 10,257 cal-mole^–1, G° is 13,063 cal-mole^–1, S° is –9.41 cal-°K^–1-mole^–1, and C _p ^o is –43 cal-°K^–1-mole^–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C).     

Salting coefficients for gases in seawater from scaled-particle theory

Experimental values of the salting coefficients for He, Ne, Ar, O₂, and N₂ in seawater are compared with values calculated from scaled-particle theory. The agreement is reasonably good; the average difference between calculated and observed values at 25°C is 0.007. Scaled-particle theory predicts correctly thatk _s should decrease as the temperature increases and that this effect should be most pronounced at low temperatures. However, the predicted magnitude ofdK _s/dt is only about half of that observed.     

Freezing temperatures and densities of solutions of some hydrocarbons and sodium oleate inN-methylacetamide. Evidence for a solvophobic interaction

The freezing temperatures and densities (at 31°C) of solutions of octane, nonane, decane, 3,3-diethylpentane, and sodium oleate inN-methylacetamide (NMA) have been measured. The molality of the freezing solution was calculated from the density. The solubilities of octane, nonane, and decane inN-methylacetamide are also reported. Apparent molal volumes calculated from the densities are close to the values in the pure hydrocarbons and are not strong functions of the concentration. This indicates the absence of any unusual packing effect. The calculated free energies of transfer of the hydrocarbons from pure hydrocarbon to NMA solution are much less negative than the corresponding values for water, showing that the bulk solvophobic interaction inN-methylacetamide is smaller than in water. This is consistent with the freezing temperatures of sodium oleate which show that micelles do not form below 0.1 mole-kg^–1. The osmotic coefficients of the hydrocarbons calculated from the freezing temperatures showed negative deviations from ideality that were larger for the hydrocarbons with the higher molecular weights. Two estimates of the pairwise solvophobic interaction inN-methylacetamide indicate that it is also smaller than in water. The solvophobic effect in this solvent does not include the large entropy and enthalpy effects found in aqueous solutions.     

葡萄糖在KRPB生理缓冲溶液中电还原反应的研究

葡萄糖在ＫＲＰＢ生理缓冲溶液中电还原反应的研究朱庆存，姜力夫，郁章玉，陈常峰，周正宇（曲阜师范大学，电化学研究所，曲阜２７３１６５）关键词：葡萄糖，扩散系数，磷酸盐生理溶液。本文从葡萄糖在铂电极上的电氧化还原峰电流与ｐＨ值的线性关系，扩散系数与葡萄糖...     

Contracted polarization functions for B to Ar

Using optimal exponents for B through Ne given by Dunning and those for Al through Ar by Woon and Dunning, d-type contracted polarization functions (2d/1d), (3d/1d), and (3d/2d) are generated from natural orbitals of atomic single and double excitation configuration interaction (SDCI) calculations, where the numbers before and after the slash are those of the primitive and contracted Gaussian type functions. The resulting contracted functions are tested on N₂ and P₂ molecules by self-consistent field and SDCI calculations, which clarify characteristics of the present polarization functions. Received: 5 June 1997 / Accepted: 20 August 1997     

疏水分配常数用于反相液相色谱保留值的预测

在反相液相色谱保留值基本方程log k_′=a+_cC_B的基础上,描述了采用疏水分配常数及氢键作用能来预测a、c参数的方法,并系统讨论了疏水分配常数对参数a、c的影响,借此对反相液相色谱宽浓度范围内的保留值进行了预测。     

Error of DIAL-measured Ozone Concentration and a Three-Wavelength Inversion Technique

Sensitivity of the error in the stratospheric ozone concentration measured by DIAL to the scattering property of the stratospheric aerosol is studied through both theoretical analysis and numerical experiment in this paper, and based on the sensitivity, a three-wavelength lidar inversion technique is proposed for a simultaneous determination of ozone concentration profile, aerosol backscatter coefficient profile and its size distribution in the stratosphere. It is found from the sensitivity study that there is a considerable effect of the stratospheric aerosol on accuracy of the ozone concentration solution. If the aerosol scattering is neglected, a large error of the solution can be obtained, especially when there is the stratospheric volcanic cloud, the error can be up to 100%. According to numerical experiments, a great improvement of the ozone concentration solution is obtained by using the present three-wavelenght inversion method.     

Determination of the diffusion coefficient of water into atelocollagen type I thin films by attenuated total reflection Fourier transform infrared spectroscopy

 The diffusion coefficient of water into thin polymer layers of glutar aldehyde cross-linked atelocollagen type I matrix (sample 1, the typical layer thickness was about 0.065 × 10⁻³ m) at 23 °C was 1.142 × 10⁻¹⁰ m² s⁻¹. At twice the concentration of the cross-linking agent (sample 2) the diffusion coefficient was 2.795 × 10⁻¹⁰ m² s⁻¹. This increase was attributed to the more ordered morphology and the creation of ordered microvoids in the film. A larger surface area is then available for the transport of diffusing molecules, allowing a higher penetration rate of the solvent. Received: 11 January 2000/Accepted: 6 May 2000