Heat and mass transfer in unsaturated porous media at a hot boundary: I. One-dimensional analytical model

We present a model of heat and mass transfer in an unsaturated zone of sand and silty clay soils, taking into account the effects of temperature gradients on the advective flux, and of the enhancement of thermal conduction by the process of latent heat transfer through vapor flow. The motivation for this study is to supply information for the planned storage of thermal energy in unsaturated soils and for hot waste storage. Information is required on the possibility of significant drying at a hot boundary, as this would reduce the thermal conductivity of a layer adjacent to the boundary and, thus, prevent effective heat transfer to the soil. This study indicates the possibility that the considered system may be unstable, with respect to the drying conditions, with the occurrence of drying depending on the initial and the boundary conditions. An analysis performed for certain boundary conditions of heat transfer and for given soil properties, disregarding the advective flux of energy, indicated that there are initial conditions of water content for which heating will not cause significant drying. Under these conditions, fine soils may be better suited for heat transfer at the hot boundary, due to their higher field capacity, although their heat conduction coefficients at saturation are lower than those of sandy soils. At present, these conclusions are limited to the range of 50–80°C. Potential effects of solute concentration at the hot boundary are indicated.     

A Quasilinear Based Procedure for Saturated/Unsaturated Water Movement in Soils

The quasilinear form of Richards equation for one-dimensional unsaturated flow in soils can be readily solved for a wide variety of conditions. However, it cannot explain saturated/unsaturated flow and the constant diffusivity assumption, used to linearise the transient quasilinear equation, can introduce significant error. This paper presents a quasi-analytical solution to transient saturated/unsaturated flow based on the quasilinear equation, with saturated flow explained by a transformed Darcy's equation. The procedure presented is based on the modified finite analytic method. With this approach, the problem domain is divided into elements, with the element equations being solutions to a constant coefficient form of the governing partial differential equation. While the element equations are based on a constant diffusivity assumption, transient diffusivity behaviour is incorporated by time stepping. Profile heterogeneity can be incorporated into the procedure by allowing flow properties to vary from element to element. Two procedures are presented for the temporal solution; a Laplace transform procedure and a finite difference scheme. An advantage of the Laplace transform procedure is the ability to incorporate transient boundary condition behaviour directly into the analytical solutions. The scheme is shown to work well for two different flow problems, for three soil types. The technique presented can yield results of high accuracy if the spatial discretisation is sufficient, or alternatively can produce approximate solutions with low computational overheads by using large sized elements. Error was shown to be stable, linearly related to element size.     

Unsaturated Transport with Linear Kinetic Sorption Under Unsteady Vertical Flow

We consider transport of a solute obeying linear kinetic sorption under unsteady flow conditions. The study relies on the vertical unsaturated flow model developed by Indelman et al. [J. Contam. Hydrol. 32 (1998), 77–97] to account for a cycle of infiltration and redistribution. One of the main features of this type of transport, as compared with the case of a continuous water infiltration, is the finite depth of solute penetration. In the infiltration stage an analytical solution that generalizes the previous results of Lassey [Water Resour. Res. 24 (1988), 343–350] and Severino and Indelman [J. Contam. Hydrol. 70 (2004), 89–115] is derived. This solution accounts for quite general initial solute distributions in both the mobile and immobile concentration. When the redistribution is also considered, two timescales become relevant, namely: (i) the desorption rate k⁻¹, and (ii) the water application time t_ap. In particular, we have assumed that the quantity ε =(k t_ap)⁻¹ can be regarded as a small parameter so that a perturbation analytical solution is obtained. At field-scale the concentration is calculated by means of the column model of Dagan and Bresler [Soil Sci. Soc. Am. J. 43 (1979), 461–467], i.e. as ensemble average over an infinite series of randomly distributed and uncorrelated soil columns. It is shown that the heterogeneity of hydraulic properties produces an additional spreading of the plume. An unusual phenomenon of plume contraction is observed at long times of solute propagation during the drying period. The mean solute penetration depth is studied with special emphasis on the impact of the variability of the saturated conductivity upon attaining the maximum solute penetration depth.     

Transition Metal Free Chemoselective Reduction of α,β‐Unsaturated Ketones to Saturated Ketones Using Tosyl Hydrazide as a Hydrogen Donor

An efficient, inexpensive and simple method for the reduction of various α,β‐unsaturated ketones to corresponding saturated ketones using tosyl hydrazide as a hydrogen donor in DMF using calcium oxide powder has been reported. A variety of enones underwent reduction without forming undesirable side products. High chemoselectivity, broad functional group tolerance and good yields are the noteworthy features of this protocol.     

金属纳米复合催化剂合成与应用的最新进展

随着纳米技术的发展,金属纳米复合材料由于其特殊的物理化学性质和潜在的催化应用受到越来越多的关注。本文系统地介绍了金属纳米复合催化剂最新的研究进展。首先,我们介绍了一些金属纳米复合催化剂的合成方法。其次,为了更好的优化催化剂的结构与催化活性的关系,并深入理解催化反应机理,我们讨论了金属纳米复合催化剂一些重要因素(包括粒子粒径、形貌、组成、载体或配体)对催化活性和选择性的影响。最后,我们进一步介绍了金属纳米复合催化剂在还原不饱和化学键中的应用(N=O,N≡C和C=O),同时还对金属纳米复合催化剂的发展方向进行了展望。     

考虑膨胀力的非饱和介质热-水-应力耦合二维有限元分析

从建立应力平衡方程、水连续性方程、能量守恒方程和弹塑性矩阵入手,使用Galerk in方法,将各控制方程分别在空间域和时间域进行离散,开发出了一个可考虑膨胀力的用于分析非饱和介质中热-水-应力耦合弹塑性问题的二维有限元程序.通过对一个假定的核废料地下处置库的热-水-应力耦合问题的数值计算,比较了无、有膨胀力时的情况,在定性上验证了该程序的正确性.     

CONSOLIDATION HEORY OF UNSATURATED SOIL BASED ON THE THEORY OF MIXTURE(Ⅰ)

Unsaturated soil is a three-phase media and is composed of soil grain,water andgas.In this paper,the consolidation problem of unsaturated soil is investigated basedon the theory of mixture.A theoretical formula of effective stress on anisotropicporous media and unsaturated soil is derived.The principle of effective stress and theprinciple of Curie symmetry are taken as two fundamental constitutive principles ofunsaturated soil.A mathematical model of consolidation of unsaturated soil isproposed,which consists of25 partial differenfial equations with25 unknowns.Withthe help of increament linearizing method,the model is reduced to5 governingequations with5 unknowns,i.e.,the three displacement components of solid phase,thepore water pressure and the pore gas pressure.7 material parameters are involved inthe model and all of them can be measured using soil tests.It is convenient to use themodel to engineering practice.The well known Biot’s theory is a special case of themodel.     

Series solutions for steady unsaturated flow in irregular porous domains

For the most part, analytical solutions for steady unsaturated infiltration have been restricted to infinite and semi-infinite seepage geometries, using the quasi-linear approximation for the hydraulic conductivity. We provide analytical series methods to solve the steady quasi-linear flow equations, in finite irregular seepage geometries. Unlike the classical approach, the series method has been modified, to cater for arbitrary boundary geometry and surface recharge distributions. The matrix flux potential and the stream function both satisfy the same governing partial differential equation, and the stream function formulation is used to estimate the series coefficients. For a finite vadose zone, the stream function solution does not uniquely determine the matrix flux potential, when flux boundary conditions are used. Consequently, the stream function solution applies to a range of moisture distributions, for given infiltration and evapotranspiration rates through the surface.     

Generalized Forchheimer Equation for Two-Phase Flow Based on Hybrid Mixture Theory

In this paper, we derive a Forchheimer-type equation for two-phase flow through an isotropic porous medium using hybrid mixture theory. Hybrid mixture theory consists of classical mixture theory applied to a multiphase system with volume averaged equations. It applies to media in which the characteristic length of each phase is small relative to the extent of the mixture. The derivation of a Forchheimer equation for single phase flow has been obtained elsewhere. These results are extended to include multiphase swelling materials which have nonnegligible interfacial thermodynamic properties.     

Novel and Efficient One Pot Condensation Reactions between Ketones and Aromatic Alcohols in the Presence of CrO3 Producing α,β‐Unsaturated Carbonyl Compounds

We report a new, effective and simple method for preparing α,β‐unsaturated carbonyl compounds by reacting ketones and aromatic alcohols at 56°C in the presence of CrO₃ (CrO₃ acts as an oxidant and also a catalyst) for around 10 h. The condensation reactions occurred effectively among a wide combination of ketones and alcohols. The procedure is simple and the yields can be high up to 98%. And a probable mechanism is proposed.