Kinetics of adsorption on activated carbon: application of heterogeneous vacancy solution theory

The kinetics of single component adsorption on activated carbon is investigated here using a heterogeneous vacancy solution theory (VST) of adsorption. The adsorption isotherm is developed to account for the adsorbate non-ideality due to the size difference between the adsorbate molecule and the vacant site, while incorporating adsorbent heterogeneity through a pore-width-related potential energy. The transport process in the bidisperse carbon considers coupled mass transfer in both macropore and micropore phases simultaneously. Adsorbate diffusion in the micropore network is modeled through effective medium theory, thus considering pore network connectivity in the adsorbent, with the activation energy for adsorbate diffusion related to the adsorption energy, represented by the Steele 10-4-3 potential for carbons. Experimental data of five hydrocarbons, CO2 and SO2 on Ajax carbon at multiple temperatures, as well as three hydrocarbons on Norit carbon at three temperatures are first fitted by the heterogeneous VST model to obtain the isotherm parameters, followed by application of the kinetic model to uptake data on carbon particles of different sizes and geometry at various temperatures. For the hydrocarbons studied, the model can successfully correlate the experimental data for both adsorption equilibrium and kinetics. However, there is some deviation in the fit of the desorption kinetics for polar compounds such as CO2 and SO2, due to the inadequacy of the L-J potential model in this case. The significance of viscous transport in the micropores is also considered here and found to be negligible, consistent with recent molecular simulation studies. (C) 2002 Elsevier Science Ltd. All rights reserved.

Field hydraulic properties of an Alfisol under various fallow systems in southwestern Nigeria

The effects of various fallow management systems and cropping intensities on water infiltration were measured on an Alfisol at Ibadan in southwestern Nigeria. The objective was to determine the influence of the land use systems (a combination of crop-fallow sequences and intercropping types) on soil hydraulic properties obtained by disc permeameter and double-ring infiltration measurements. The experiment was established in 1989 as a split-plot design with four replications. The main plots were natural fallow, planted Pueraria phaseoloides and planted Leucaena leucocephala. The subplots were 1 year of maize/cassava intercrop followed by 3-year fallow (25% cropping intensity), or 2-year fallow (33% cropping intensity), or 1-year fallow (50% cropping intensity), or no fallow period (100% cropping intensity). Water infiltration rates and sorptivities were measured under saturated and unsaturated flow. Irrespective of land use, infiltration rates at the soil surface (121-324 cm h(-1)) were greater than those measured at 30 cm depth (55-144 cm h(-1)). This indicated that fewer large pores were present below 30 cm depth compared with 0-30 cm, depth. Despite some temporal variation, sorptivities with the highest mean value of 93.5 cm h(-1/2) increased as the cropping intensity decreased, suggesting a more continuous macropore system under less intensive land use systems. This was most likely due to continuous biopores created by perennial vegetation under long fallow systems. Intercropped maize and cassava yields also increased as cropping intensity decreased. The weak relationship between crop yields and hydraulic conductivity/infiltration rates suggests that the rates were not limiting.

Analysis of multicomponent adsorption kinetics on activated carbon

An integrated mathematical model for the kinetics of multicomponent adsorption on microporous carbon was developed. Transport in this bidisperse solid is represented by balance equations in the macropore and micropore phases, in which gas-phase diffusion dominates the mass transfer in the macropores, with the phenomenological diffusivities represented by the generalized Maxwell-Stefan (GMS) formulation. Viscous flow also contributes to the macropore fluxes and is included in the MS expressions. Diffusion of the adsorbed phase controls the mass transfer in the micro ore phase, p which is also described in a similar way by the MS method. The adsorption isotherms are represented by a new heterogeneous modified vacancy solution theory formulation of adsorption, which has proved to be a robust method for adsorption on activated carbons. The model is applied to the coadsorption and codesorption of C2H6 and C3H8 on Ajax and Norit carbon, as well as the displacement on Ajax carbon. The effect of the viscous flow in the macropore phase is not significant for the cases studied. The model accurately predicts the overshoot behavior and rollup of C2H6 during coadsorption. The prediction for the heavier compound C3H8 is always satisfactory, though at higher C3H8 mole fraction, the overshoot extent of C2H6 is overpredicted, possibly due to neglect of heat effects.

Repair of non-circumferential cervical trachea defects by three different latissimus dorsi flaps. A comparative studyin an experimental setting.

BACKGROUND: Large intrathoracic airway defects may be closed using a pedicled latissimus dorsi (LD) flap, with rewarding results. This study addresses the question of whether this holds true for extrathoracic non-circumferential tracheal defects. METHODS: A cervical segment of the trachea of 4 x 1 cm was resected in 9 white male pigs. The defect was stented with a silicone stent for 3 months and closed either by an LD flap alone (group a, n = 3), an LD flap with an attached rib segment covered by pleura (group b, n = 3), or an LD flap reinforced by a perforated polylactide (MacroPore) plate (group c, n = 3). The trachea was assessed by rigid endoscopy at 3 and 4 months and histologically at 4 months postoperatively. RESULTS: The degree of stenosis at the level of the reconstruction at 4 months was 25, 50 and 75% in group a, 15, 50 and 60% in group b, and 20, 95 and 95% in group c, respectively. The percentage of the defect covered by columnar epithelium was 100% in all animals of group a, 60, 100 and 100% in group b, and 10, 0 and 0% in group c. Resorption of the rib was seen in all animals of group b and obstructive inflammatory polyps were found in 2 animals of group c. CONCLUSION: Pedicled LD flaps provided less satisfactory results for closure of large non-circumferential extrathoracic airway defects than observed after intrathoracic reconstruction. A pedicled rib segment added to the LD flap did not improve the results obtained from LD flap repair alone, and an embedded MacroPore prosthesis may result in severe airway stenosis due to plate migration and intense inflammatory reaction protruding into the tracheal lumen.

Method to estimate soil macroporosity and microporosity based on sand content and bulk density

Macroporosity is often used in the determination of soil compaction. Reduced macroporosity can lead to poor drainage, low root aeration and soil degradation. The aim of this study was to develop and test different models to estimate macro and microporosity efficiently, using multiple regression. Ten soils were selected within a large range of textures: sand (Sa) 0.07-0.84; silt 0.03-0.24; clay 0.13-0.78 kg kg-1 and subjected to three compaction levels (three bulk densities, BD). Two models with similar accuracy were selected, with a mean error of about 0.02 m³ m-3 (2 %). The model y = a + b.BD + c.Sa, named model 2, was selected for its simplicity to estimate Macro (Ma), Micro (Mi) or total porosity (TP): Ma = 0.693 - 0.465 BD + 0.212 Sa; Mi = 0.337 + 0.120 BD - 0.294 Sa; TP = 1.030 - 0.345 BD 0.082 Sa; porosity values were expressed in m³ m-3; BD in kg dm-3; and Sa in kg kg-1. The model was tested with 76 datum set of several other authors. An error of about 0.04 m³ m-3 (4 %) was observed. Simulations of variations in BD as a function of Sa are presented for Ma = 0 and Ma = 0.10 (10 %). The macroporosity equation was remodeled to obtain other compaction indexes: a) to simulate maximum bulk density (MBD) as a function of Sa (Equation 11), in agreement with literature data; b) to simulate relative bulk density (RBD) as a function of BD and Sa (Equation 13); c) another model to simulate RBD as a function of Ma and Sa (Equation 16), confirming the independence of this variable in relation to Sa for a fixed value of macroporosity and, also, proving the hypothesis of Hakansson & Lipiec that RBD = 0.87 corresponds approximately to 10 % macroporosity (Ma = 0.10 m³ m-3).

Sampling Position under No-Tillage System Affects the Results of Soil Physical Properties

ABSTRACT Understanding the spatial behavior of soil physical properties under no-tillage system (NT) is required for the adoption and maintenance of a sustainable soil management system. The aims of this study were to quantify soil bulk density (BD), porosity in the soil macropore domain (PORp) and in the soil matrix domain (PORm), air capacity in the soil matrix (ACm), field capacity (FC), and soil water storage capacity (FC/TP) in the row (R), interrow (IR), and intermediate position between R and IR (designated IP) in the 0.0-0.10 and 0.10-0.20 m soil layers under NT; and to verify if these soil properties have systematic variation in sampling positions related to rows and interrows of corn. Soil sampling was carried out in transect perpendicular to the corn rows in which 40 sampling points were selected at each position (R, IR, IP) and in each soil layer, obtaining undisturbed samples to determine the aforementioned soil physical properties. The influence of sampling position on systematic variation of soil physical properties was evaluated by spectral analysis. In the 0.0-0.1 m layer, tilling the crop rows at the time of planting led to differences in BD, PORp, ACm, FC and FC/TP only in the R position. In the R position, the FC/TP ratio was considered close to ideal (0.66), indicating good water and air availability at this sampling position. The R position also showed BD values lower than the critical bulk density that restricts root growth, suggesting good soil physical conditions for seed germination and plant establishment. Spectral analysis indicated that there was systematic variation in soil physical properties evaluated in the 0.0-0.1 m layer, except for PORm. These results indicated that the soil physical properties evaluated in the 0.0-0.1 m layer were associated with soil position in the rows and interrows of corn. Thus, proper assessment of soil physical properties under NT must take into consideration the sampling positions and previous location of crop rows and interrows.

Qualidade física de um latossolo vermelho acriférrico sob diferentes sistemas de uso e manejo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural features of silicas prepared in n-heptane/water/ethanol/sodium dodecylsulfate microemulsions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Efficiency of ethanol conversion induced by controlled modification of pore structure and acidic properties of alumina catalysts

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of the quality index of a Paleudult under sunflower culture and different management systems

Soil is an essential resource for life and its properties are susceptible to be modified by tillage systems. The impact of management practices on soil functions can be assessed through a soil quality index. It is interesting to assess soil quality in different soil types. Therefore, the aim of this study was to determine the soil quality index of a Paleudult under different management conditions and sunflower culture. The experiment was carried out in Botucatu (SP, Brazil), in an 11-year non-tilled area used for growing soybean and maize during summer and black oat or triticale in winter. Four management systems were considered: no-tillage with a hoe planter (NTh), no-tillage with a double-disk planter (NTd), reduced tillage (RT) and conventional tillage (CT). Soil samples were taken from the planting lines at harvest time. To determine the soil quality indices, following the methodology proposed by Karlen and Stott (1994), three main soil functions were assessed: soil capacity for root development, water storage capacity of the soil and nutrient supply capacity of the soil. The studied Paleudult was considered a soil with good quality under all the observed management systems. However, the soil quality indices varied between treatments being 0.64, 0.68, 0.86 and 0.79 under NTh, NTd, RT and CT, respectively. Physical attributes such as resistance to penetration and macroporosity increased the soil quality index in RT and CT compared to NTh and NTd. The soil quality indices obtained suggested that the evaluated soil is adequate for sunflower production under our study conditions. In view of the SQI values, RT is the most suitable management for this site since it preserves soil quality and provides an acceptable sunflower yield. © 2011 Elsevier B.V.

Porous silica matrix obtained from pyrex class by hydrothermal treatment: Characterization and nature of the porosity

A novel porous silica matrix has been prepared from Pyrex glass, using hydrothermal treatment under saturated-steam condition. This process makes it possible to obtain, in one step, a silica support formed of a homogeneously distributed and interconnected macropore microstructure. The new matrix contains silanol groups that can be used in reactions of surface modification to provide a hybrid material and a selective macrofiltration membrane, and also it can improve chemical inertness. The porous matrix is noncrystalline as obtained and, after thermal treatment at temperatures higher than 950degreesC, exhibits an X-ray pattern characteristic of alpha-cristobalite and low volume contraction. The present samples were characterized by scanning electron microscopy, mercury intrusion porosimetry, nitrogen adsorption-desorption isotherms, infrared spectroscopy, X-ray powder diffractometry, atomic absorption, and high-resolution solid-state nuclear magnetic resonance. The results present a new way of producing a macroporous silica matrix.

Atributos químicos e físicos de um argissolo cultivado com Panicum maximum Jacq. cv. IPR-86 Milênio, sob lotação rotacionada e adubado com nitrogênio

A avaliação dos atributos químicos e físicos do solo é necessária em estudos que exploram intensivamente os sistemas de pastejo. No presente trabalho, objetivou-se avaliar as variações nos atributos físicos e químicos de um Argissolo cultivado com capim-milênio, sob pastejo, no intervalo compreendido entre outubro/2001 e maio/2002, no quinto ano de aplicação sucessiva das seguintes doses de N: 0, 150, 300 e 450 kg ha-1. Após os cinco anos de aplicação de 450 kg ha-1 de N, o teor de MO aumentou em 5 g dm-3, o que resultou em aumento da CTC. No período de outubro/2001 a maio/2002 houve diminuição nos valores de pH e de V com a aplicação de N. A densidade do solo variou pouco com a adubação nitrogenada; a percentagem de microporos aumentou e a de macroporos diminuiu na camada de 0-5 cm com o aumento das doses de N, mas a porosidade total permaneceu constante; e a resistência à penetração, quando o solo apresentava 90 g kg-1 de água, não foi afetada pelas doses de N e não foi restritiva ao crescimento das plantas.

Viscous-Flow Approach to In Situ Infiltration and In Vitro Saturated Hydraulic Conductivity Determination

Infiltration is dominantly gravity driven, and a viscous-flow approach was developed. Laminar film flow equilibrates gravity with the viscous force and a constant flow velocity evolves during a period lasting 3/2 times the duration of a constant input rate, qS. Film thickness F and the specific contact area L of the film per unit soil volume are the key parameters. Sprinkler irrigation produced in situ time series of volumetric water contents, θ(z,t), as determined with TDR probes. The wetting front velocity v and the time series of the mobile water content, w(z,t) were deduced from θ(z,t). In vitro steady flow in a core of saturated soil provided volume flux density, q(z,t), and flow velocity, v, as determined from a heat front velocity. The F and L parameters of the in situ and the in vitro experiments were compared. The macropore-flow restriction states that, for a particular permeable medium, the specific contact area L must be independent from qS i.e., dL/dqS = 0. If true, then the relationship of qS ∝ v3/2 could scale a wide range of input rates 0 ≤ qS ≤ saturated hydraulic conductivity, Ksat, into a permeable medium, and kinematic-wave theory would become a versatile tool to deal with non-equilibrium flow. The viscous-flow approach is based on hydromechanical principles similar to Darcy’s law, but currently it is not suited to deduce flow properties from specified individual spatial structures of permeable media.

Physical properties and AMS characteristics of ODP Site 185-1149 sediments

During Ocean Drilling Program Leg 185, we studied progressive changes of microfabrics of unconsolidated pelagic and hemipelagic sediments in Holes 1149A and 1149B in the northwest Pacific at 5818 m water depth. We paid particular attention to the early consolidation and diagenetic processes without tectonic deformation before the Pacific plate subduction at the Izu-Bonin Trench. Shape, size, and arrangement of pores were analyzed by scanning electron microscope (SEM) and were compared to anisotropy of magnetic susceptibility (AMS) data. The microfabric in Unit I is nondirectional fabric and is characterized by large peds of ~10-100 µm diameter, which are made up of clay platelets (mainly illite) and siliceous biogenic fragments. They are ovoid in shape and are mechanically packed by benthic animals. Porosity decreases from 0 to 60 meters below seafloor (mbsf) in Unit I (from 60% to 50%) in association with macropore size decreases. The microfabric of coarser grain particles other than clay in Unit II is characterized by horizontal preferred orientation because of depositional processes in Subunit IIA and burial compaction in Subunit IIB. On the other hand, small peds, which are probably made of fragments of fecal pellets and are composed of smectite and illite (3-30 µm diameter), are characterized by random orientation of clay platelets. The clay platelets in the small peds in Subunit IIA are in low-angle edge-to-face (EF) or face-to-face (FF) contact. These peds are electrostatically connected by long-chained clay platelets, which are interconnected by high-angle EF contact. Breaking of these long chains by overburden pressure diminishes the macropores, and the clay platelets in the peds become FF in contact, resulting in decreases in the volume of the micropores between clay platelets. Thus, porosity in Subunits IIA and IIB decreases remarkably downward. The AMS indicates random fabric and horizontal preferred orientation fabric in Units I and II, respectively. This result corresponds to that of SEM microfabric observations.In Subunit IIB, pressure solutions around radiolarian tests and clinoptilolite veins with normal displacement sense are seen distinctively below ~170 mbsf, probably in correspondence to the transition zone from opal-A to opal-CT.

Effects of adsorbed phase on diffusion of subcritical hydrocarbons in activated carbon at low pressures

Diffusions of free and adsorbed molecules of subcritical hydrocarbons in activated carbon were investigated to study the influence of adsorbed molecules on both diffusion processes at low pressures. A collision reflection factor, defined as the fraction of molecules undergoing collision to the solid surface over reflection from the surface, is incorporated into Knudsen diffusivity and surface diffusivity in meso/macropores. Since the porous structure of activated carbon is bimodal in nature, the diffusion of adsorbed molecules is contributed by that of weakly adsorbed molecules on the meso/macropore surfaces and that of strongly adsorbed molecules in the small confinement of micropores. The mobility of adsorbed molecules on the meso/macropore surface is characterized by the surface diffusivity D-mu 2, while that in the micropore is characterized by D-mu 1. In our study with subcritical hydrocarbons, we have found that the former increases almost linearly with pressure, while the latter exhibits a sharp increase at a very low-pressure region and then decreases beyond a critical pressure. This critical pressure is identified as a pressure at which the micropores are saturated.