Electrophilic Addition Reaction of Ethene with Hydrogen Chloride on Cold Molecular Films: Evidence of Ethyl Cationic Intermediate

We studied the initial‐stage mechanism of the electrophilic addition reaction of ethene with HCl by examining the interactions between ethene and HCl on water‐ice and frozen molecular films at temperatures of 80–140 K. Cs⁺ reactive ion scattering (RIS) and low‐energy sputtering (LES) techniques were used to probe the reaction intermediates that were kinetically trapped on the surface, in conjunction with temperature‐programmed desorption (TPD) mass spectrometry to monitor the desorbing species. The reaction initially produced the π complex of HCl and ethene at temperatures below about 93 K and an “ethyl cationic species” at temperatures below about 100 K. The ethyl cationic species was formed via direct proton transfer from the HCl molecule to ethene with the assistance of water solvation, rather than via the interaction of hydronium ions and ethene. At high temperatures, this species dissociated into ethene and hydronium and chloride ions. The reaction did not, however, complete the final transition state on the ice surface to produce ethyl chloride. The observation gives evidence that the electrophilic addition reaction of ethene occurs through an ethyl‐like intermediate with an ionic character.     

不同积雪深度与面积对积雪覆盖遥感反演的影响

针对利用多源遥感数据进行积雪覆盖监测的需要,在分析不同深度与面积的积雪实测光谱基础上,探讨了在利用NDSI方法进行积雪覆盖遥感监测时,不同积雪深度对其的影响,并以HJ-1B卫星以及MODIS卫星为例,研究了不同积雪面积对遥感积雪反演的影响。结果表明,积雪深度几乎对遥感积雪覆盖监测的结果没有影响,而在积雪面积方面,受所使用的遥感影像空间分辨率的制约,对遥感积雪监测的结果有一定影响。     

降低真空制冰系统真空度的理论研究

文中针对真空冰浆制备系统运行真空度较高的问题进行分析,提出利用在水中加入中介物质的方法来降低制备系统对真空度的要求,并利用物质的化学势平衡理论与溶液相图相结合的方法,从理论上验证了在真空冰浆制备系统中加入中介物质具有降低系统对真空度要求的作用.     

电容感应式冰厚监测系统在南极海冰监测中的应用

为了实现对南极的实时自动化监测,设计并研制了电容式冰厚监测系统,系统于2012年3月至8月对南极中山站附近的近岸海冰进行了连续6个月的厚度自动化监测,通过对监测数据的对比分析,得到了监测系统的准确度与相对偏差.结果证明系统用于高精度定点监测海冰厚度是可行的,并对系统监测南极海冰的不足与今后改进研究的内容进行了讨论.     

Finite 2‐Geodesic Transitive Graphs of Prime Valency

We classify noncomplete prime valency graphs satisfying the property that their automorphism group is transitive on both the set of arcs and the set of 2‐geodesics. We prove that either Γ is 2‐arc transitive or the valency p satisfies , and for each such prime there is a unique graph with this property: it is a nonbipartite antipodal double cover of the complete graph with automorphism group and diameter 3.     

An optimal switching approach toward cost‐effective control of a stand‐alone photovoltaic panel system under stochastic environment

The operation of a stand‐alone photovoltaic (PV) system ultimately aims for the optimization of its energy storage. We present a mathematical model for cost‐effective control of a stand‐alone system based on a PV panel equipped with an angle adjustment device. The model is based on viscosity solutions to partial differential equations, which serve as a new and mathematically rigorous tool for modeling, analyzing, and controlling PV systems. We formulate a stochastic optimal switching problem of the panel angle, which is here a binary variable to be dynamically controlled under stochastic weather condition. The stochasticity comes from cloud cover dynamics, which is modeled with a nonlinear stochastic differential equation. In finding the optimal control policy of the panel angle, switching the angle is subject to impulsive cost and reduces to solving a system of Hamilton‐Jacobi‐Bellman quasi‐variational inequalities (HJBQVIs). We show that the stochastic differential equation is well posed and that the HJBQVIs admit a unique viscosity solution. In addition, a finite‐difference scheme is proposed for the numerical discretization of HJBQVIs. A demonstrative computational example of the HJBQVIs, with emphasis on a stand‐alone experimental system, is finally presented with practical implications for its cost‐effective operation.     

Determination of trace level of perchlorate in Antarctic snow and ice by ion chromatography coupled with tandem mass spectrometry using an automated sample on-line preconcentration method

A new ion chromatography coupled with tandem mass spectrometry（IC-ESI-MS/MS） method,with automated sampling and on-line preconcentration,has been developed for the determination of perchlorate in Antarctic snow and ice at low part-per-trillion（ng/L） levels.To the best of our knowledge, this is the first time that an analytical method is used for the determination of perchlorate in Antarctic snow and ice.The IC-ESI-MS/MS instrumentation consisted of an ICS2000 ion chromatography（IC） system coupled to an API3200 electrospray tandem mass spectrometer（ESI-MS/MS）.On-line preconcentration was realized through a six-port injector valve,a TAC-ULP1 concentrator column and an AS auto-sampler.Multiple reaction monitoring（MRM） mode was used to quantify the perchlorate anion.The transition of ³⁵Cl¹⁶O₄^-（m/z 98.9） into ³⁵Cl¹⁶O₃^-（m/z 82.9） was monitored for quantifying the main analyte,and the transition of ³⁷Cl¹⁶O₄^-（m/z 100.9） into ³⁷Cl¹⁶O₃^-（m/z 84.9） was monitored for examining a proper isotopic abundance ratio of ³⁵Cl to ³⁷Cl,which was used as a confirmation tool.The limit of detection（LOD） and limit of quantitation（LOQ） for the method was 0.2 ng/ L and 0.5 ng/L,respectively.And this new method exhibited acceptable accuracy and precision for samples at ng/L levels.All the tested snow and ice samples were found to contain measurable amount of perchlorate,ranging from 10 ng/L to 340 ng/L.     

Impact of ice particle shape on short-wave radiative forcing: A case study for an arctic ice cloud

We used four different non-spherical particle models to compute optical properties of an arctic ice cloud and to simulate corresponding cloud radiative forcings and fluxes. One important finding is that differences in cloud forcing, downward flux at the surface, and absorbed flux in the atmosphere resulting from the use of the four different ice cloud particle models are comparable to differences in these quantities resulting from changing the surface albedo from 0.4 to 0.8, or by varying the ice water content (IWC) by a factor of 2. These findings show that the use of a suitable non-spherical ice cloud particle model is very important for a realistic assessment of the radiative impact of arctic ice clouds. The differences in radiative broadband fluxes predicted by the four different particle models were found to be caused mainly by differences in the optical depth and the asymmetry parameter. These two parameters were found to have nearly the same impact on the predicted cloud forcing. Computations were performed first by assuming a given vertical profile of the particle number density, then by assuming a given profile of the IWC. In both cases, the differences between the cloud radiative forcings computed with the four different non-spherical particle models were found to be of comparable magnitude. This finding shows that precise knowledge of ice particle number density or particle mass is not sufficient for accurate prediction of ice cloud radiative forcing. It is equally important to employ a non-spherical shape model that accurately reproduces the ice particle's dimension-to-volume ratio and its asymmetry parameter. The hexagonal column/plate model with air-bubble inclusions seems to offer the highest degree of flexibility.     

长柱状气溶胶粒子的光散射特性

以中纬度卷云中常见的长柱状冰晶为例,利用长柱状粒子光散射理论,探讨了入射光为线偏振时,电矢量平行和垂直于入射面情况下,单个长柱状粒子的散射光强度分布和偏振特性随入射角、尺度参数与偏振态的转化关系:随着入射角的增大,散射强度、偏振总体趋于对称且数值振荡频率降低,散射强度总体减小,偏振的改变程度总体增大;随着尺度参数的增大,散射强度、偏振的数值振荡频率增大,散射强度数值振荡峰的幅度整体减小,电矢量平行于粒子长轴时主偏振的数量、强度和位置皆有变迁,电矢量垂直于粒子长轴时前后主偏振位置相对固定;随着偏振度的减小,散射强度、偏振趋向于一致,两者的数值改变程度减小,当偏振度减小到0时,散射强度、偏振变得完全相同。选取火山尘埃和烟灰与冰晶对比,阐述了粒子散射光的强度分布和偏振特性随折射率的变化规律:折射率虚部不改变散射强度的整体趋势,但使散射强度和偏振的振荡峰幅度增大,当其数值较大时,使得偏振的数值振荡峰覆盖范围拓宽。