Fluid-Fluid Reactions: Study of the Surface Renewal Theory in Chemical Engineering Courses

The Surface Renewal Theory (SRT) is one of the most unfamiliar models in order to characterize fluid-fluid and fluid-fluid-solid reactions, which are of considerable industrial and academicals importance. In the present work, an approach to the resolution of the SRT model by numerical methods is presented, enabling the visualization of the influence of different variables which control the heterogeneous overall process. Its use in a classroom allowed the students to reach a great understanding of the process.

Bifurcation Analysis of Reaction Diffusion Systems on Arbitrary Surfaces

In this article we present a computational framework for isolating spatial patterns arising in the steady states of reaction-diffusion systems. Such systems have been used to model many different phenomena in areas such as developmental and cancer biology, cell motility and material science. Often one is interested in identifying parameters which will lead to a particular pattern. To attempt to answer this, we compute eigenpairs of the Laplacian on a variety of domains and use linear stability analysis to determine parameter values for the system that will lead to spatially inhomogeneous steady states whose patterns correspond to particular eigenfunctions. This method has previously been used on domains and surfaces where the eigenvalues and eigenfunctions are found analytically in closed form. Our contribution to this methodology is that we numerically compute eigenpairs on arbitrary domains and surfaces. Here we present various examples and demonstrate that mode isolation is straightforward especially for low eigenvalues. Additionally we see that if two or more eigenvalues are in a permissible range then the inhomogeneous steady state can be a linear combination of the respective eigenfunctions. Finally we show an example which suggests that pattern formation is robust on similar surfaces in cases that the surface either has or does not have a boundary.

Dissolved iron measured along surface transects of the CARUSO-EISENEX experiment

Measurements of Fe(II) and H2O2 were carried out in the Atlantic sector of the Southern Ocean during EisenEx, an iron enrichment experiment. Iron was added on three separate occasions, approximately every 8 days, as a ferrous sulfate (FeSO4) solution. Vertical profiles of Fe(II) showed maxima consistent with the plume of the iron infusion. While H2O2 profiles revealed a corresponding minima showing the effect of oxidation of Fe(II) by H2O2, observations showed detectable Fe(II) concentrations existed for up to 8 days after an iron infusion. H2O2 concentrations increased at the depth of the chlorophyll maximum when iron concentrations returned to pre-infusion concentrations (<80 pM) possibly due to biological production related to iron reductase activity. In this work, Fe(II) and dissolved iron were used as tracers themselves for subsequent iron infusions when no further SF6 was added. EisenEx was subject to periods of weak and strong mixing. Slow mixing after the second infusion allowed significant concentrations of Fe(II) and Fe to exist for several days. During this time, dissolved and total iron in the infusion plume behaved almost conservatively as it was trapped between a relict mixed layer and a new rain-induced mixed layer. Using dissolved iron, a value for the vertical diffusion coefficient Kz=6.7±0.7 cm**2/s was obtained for this 2-day period. During a subsequent surface survey of the iron-enriched patch, elevated levels of Fe(II) were found in surface waters presumably from Fe(II) dissolved in the rainwater that was falling at this time. Model results suggest that the reaction between uncomplexed Fe(III) and O2? was a significant source of Fe(II) during EisenEx and helped to maintain high levels of Fe(II) in the water column. This phenomenon may occur in iron enrichment experiments when two conditions are met: (i) When Fe is added to a system already saturated with regard to organic complexation and (ii) when mixing processes are slow, thereby reducing the dispersion of iron into under-saturated waters.

Radium in Arctic surface water

The transpolar drift is strongly enriched in 228Ra accumulated on the wide Arctic shelves with subsequent rapid offshore transport. We present new data of Polarstern expeditions to the central Arctic and to the Kara and Laptev seas. Because 226Ra activities in Pacific waters are 30% higher than in Atlantic waters, we correct 226Ra for the Pacific admixture when normalizing 228Ra with 226Ra. The use of 228Ra decay as age marker critically depends on the constancy in space and time of the source activity, a condition that has not yet adequately been tested. While 228Ra decays during transit over the central basin, ingrowth of 228Th could provide an alternative age marker. The high 228Th/228Ra activity ratio (AR = 0.8-1.0) in the central basins is incompatible with a mixing model based on horizontal eddy diffusion. An advective model predicts that 228Th grows to an equilibrium AR, the value of which depends on the scavenging regime. The low AR over the Lomonosov Ridge (AR = 0.5) can be due to either rapid transport (minimum age without scavenging 1.1 year) or enhanced scavenging. Suspended particulate matter load (derived from beam transmission and particulate 234Th) and total 234Th depletion data show that scavenging, although extremely low in the central Arctic, is enhanced over the Lomonosov Ridge, making an age of 3 years more likely. The combined data of 228Ra decay and 228Th ingrowth confirm the existence of a recirculating gyre in the surface water of the eastern Eurasian Basin with a river water residence time of at least 3 years.

Distribution of melamine in polyester-melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester-melamine thermoset coatings during curing has been investigated with X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (

NMR imaging of the diffusion of water at 310 K into semi-IPNs of PEM and Poly(HEMA-co-THFMA)

Magnetic resonance imaging has been used to monitor the diffusion of water at 310 K into a series of semi-IPNs of poly(ethyl methacrylate), PEM, and copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA. The diffusion was found to be well described by a Fickian kinetic model in the early stages of the water sorption process, and the diffusion coefficients were found to be slightly smaller than those for the copolymers of HEMA and THFMA, P(HEMA-co-THFMA), containing the same mole fraction of HEMA in the matrix. A second stage sorption process was identified in the later stage of water sorption by the PEM/PTHFMA semi-IPN and for the systems containing a P(HEMA-co-THFMA) component with a mole fraction HEMA of 0.6 or less. This was characterized by the presence of Water near the surface of the cylinders with a longer NMR T-2 relaxation time, which would be characteristic of mobile water, such as water present in large pores or surface fissures. The presence of the drug chlorhexidine in the polymer matrixes at a concentration of 5.625 wt % was found not to modify the properties significantly, but the diffusion coefficients for the water sorption were systematically smaller when the drug was present.

Patch and whole of surface mass-transfer rate measurements on a stepped rotating cylinder electrode

A recently developed whole of surface electroplating technique was used to obtain mass-transfer rates in the separated flow region of a stepped rotating cylinder electrode. These data are compared with previously reported mass-transfer rates obtained with a patch electrode. It was found that the two methods yield different results, where at lower Reynolds numbers, the mass-transfer rate enhancement was noticeably higher for the whole of the surface electrode than for the patch electrode. The location of the peak mass transfer behind the step, as measured with a patch electrode, was reported to be independent of the Reynolds number in previous studies, whereas the whole of the surface electrode shows a definite Reynolds number dependence. Large eddy simulation results for the recirculating region behind a step are used in this work to show that this difference in behavior is related to the existence of a much thinner fluid layer at the wall for which the velocity is a linear junction of distance from the wall. Consequently, the diffusion layer no longer lies well within a laminar sublayer. It is concluded that the patch electrode responds to the wall shear stress for smooth wall flow as well as for the disturbed flow region behind the step. When the whole of the surface is electro-active, the response is to mass transfer even when this is not a sole function of wall shear stress. The results demonstrate that the choice of the mass-transfer measurement technique in corrosion studies can have a significant effect on the results obtained from empirical data.

Dissipation of acetochlor and its distribution in surface and sub-surface soil fractions during laboratory incubations

Pesticides in soil are subject to a number of processes that result in transformation and biodegradation, sorption to and desorption from soil components, and diffusion and leaching. Pesticides leaching through a soil profile will be exposed to changing environmental conditions as different horizons with distinct physical, chemical and biological properties are encountered. The many ways in which soil properties influence pesticide retention and degradation need to be addressed to allow accurate predictions of environmental fate and the potential for groundwater pollution. Degradation and sorption processes were investigated in a long-term (100 days) study of the chloroacetanilide herbicide, acetochlor. Soil cores were collected from a clay soil profile and samples taken from 0-30cm (surface), 1.0-1.3m (mid) and 2.7-3.0m (deep) and treated with acetochlor (2.5, 1.25, 0.67 mu g acetochlor g(-1) dry wt soil, respectively). In sterile and non-sterile conditions, acetochlor concentration in the aqueous phase declined rapidly from the surface and subsoil layers, predominantly through nonextractable residue (NER) formation on soil surfaces, but also through biodegradation and biotic transformation. Abiotic transformation was also evident in the sterile soils. Several metabolites were produced, including acetochlor-ethane sulphonic acid and acetochlor-oxanilic acid. Transformation was principally microbial in origin, as shown by the differences between non-sterile and sterile soils. NER formation increased rapidly over the first 21 days in all soils and was mainly associated with the macroaggregate (> 2000 mu m diameter) size fractions. It is likely that acetochlor is incorporated into the macroaggregates through oxidative coupling, as humification of particulate organic matter progresses. The dissipation (ie total loss of acetochlor) half-life values were 9.3 (surface), 12.3 (mid) and 12.6 days (deep) in the non-sterile soils, compared with 20.9 [surface], 23.5 [mid], and 24 days [deep] in the sterile soils, demonstrating the importance of microbially driven processes in the rapid dissipation of acetochlor in soil.

Catalytic effects of subsurface carbon in the chemisorption of hydrogen on a Mg(0001) surface: an ab-initio study

Ab initio density functional theory (DFT) calculations are performed to explore possible catalytic effects on the dissociative chemisorption of hydrogen on a Mg(0001) surface when carbon is incorporated into Mg materials. The computational results imply that a C atom located initially on a Mg(0001) surface can migrate into the subsurface and occupy an fcc interstitial site, with charge transfer to the C atom from neighboring Mg atoms. The effect of subsurface C on the dissociation of H-2 on the Mg(0001) surface is found to be relatively marginal: a perfect sublayer of interstitial C is calculated to lower the barrier by 0.16 eV compared with that on a pure Mg(0001) surface. Further calculations reveal, however, that sublayer C may have a significant effect in enhancing the diffusion of atomic hydrogen into the sublayers through fcc channels. This contributes new physical understanding toward rationalizing the experimentally observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

NMR microscopy: A tool for measuring monomer diffusion in supercritical CO2

The diffusion of styrene into linear low density polyethylene in a solution of supercritical CO2 was investigated using NMR microimaging. For both pure styrene and styrene dissolved in supercritical CO2, the diffusion was found to follow Fickian kinetics. Supercritical CO2 was found to enhance the rate and extent of diffusion of styrene into the substrate by up to three times under the conditions of this investigation, compared to pure styrene. NMR imaging was used to measure the concentration profiles of the styrene penetrants in real time, and the results were fitted to a Fickian model for diffusion. At a CO2 pressure of 150 bar and temperature of 40 degrees C, the diffusion coefficient of a 30 wt-% solution of styrene into LLDPE was calculated to be 1 X 10(-11) m(2). s(-1). This is significantly faster than the diffusion coefficient measured for pure styrene diffusion at 40 degrees C (3 x 10(-12) m(2). s(-1)). The diffusion coefficients determined by gravimetric analysis were slightly higher than those determined by the imaging method. This was probably due to residual styrene and/or polystyrene adhering to the surface of the films in the gravimetric technique.

Incorporating level set methods in Geographical Information Systems (GIS) for land-surface process modelling

Land-surface processes include a broad class of models that operate at a landscape scale. Current modelling approaches tend to be specialised towards one type of process, yet it is the interaction of processes that is increasing seen as important to obtain a more integrated approach to land management. This paper presents a technique and a tool that may be applied generically to landscape processes. The technique tracks moving interfaces across landscapes for processes such as water flow, biochemical diffusion, and plant dispersal. Its theoretical development applies a Lagrangian approach to motion over a Eulerian grid space by tracking quantities across a landscape as an evolving front. An algorithm for this technique, called level set method, is implemented in a geographical information system (GIS). It fits with a field data model in GIS and is implemented as operators in map algebra. The paper describes an implementation of the level set methods in a map algebra programming language, called MapScript, and gives example program scripts for applications in ecology and hydrology.

Polymer modified cement: hydration microstructure and diffusion properties

Investigations concentrated on the styrene butadiene rubber (SBR) latex and formulations included standard carboxylated and special carboxylated latexes. The aqueous component, containing the stabilisers and antifoaming agent but not the polymer solids, was also used. For comparison, limited investigations were carried out using other polymer types e.g. acrylic, ethylene-vinyl acetate (EVA), and redispersible powders rather than emulsions. The major findings were: 1) All latex systems investigated acted as retarders for cement hydration. The extent of retardation depends on the type of polymer. The mechanism for cement hydration may be changed, and excessive retardation influences properties. 2) Polymer modified cements exhibited either similar or coarser pore structures compared with unmodified cements. Results suggest that polymer mainly exists in a mixture of cement hydrates and polymer phase. Very little evidence was found for the formation of a distinct polymer film phase. 3) During the first few days of curing the polymer solids are removed from the pore solution and concentrations of OH-, Na+ and K+ are reduced. These observations are probably a result of polymer-cement surface interactions since there was no evidence of any chemical reactions or degradation of the polymer. 4) Improved diffusional resistance of modified cements depends on the ability to achieve adequate workability at low w/c ratio, rather than modification of matrix structure.

Inorganic surface treatments for concrete protection

Carbonated cement paste surfaces were characterised prior to application of surface treatments. Their chemical and physical properties varied with distance from the surface and method of carbonation. From the surface inwards the pH of expressed pore solutions and porosity were observed to increase. Hardness increased after natural carbonation, but decreased after accelerated carbonation. Generally, accelerated carbonation caused more extreme changes. Investigations were carried out on four concrete surface hardening treatments; two sodium silicates and two silicofluorides. These treatments penetrated and hardened the surface of naturally dried uncarbonated cement paste to a depth fo 250m. Silicofluorides reacted with uncarbonated and carbonated cement pastes to form calcium fluoride. The question of how sodium silicates harden the surface remains unanswered. Surface hardeners do not significantly affect the rate of carbonation, and are unsuitable for re-alkalising carbonated cement paste. Water repellent treatments studied include a silane, a siloxane and a silicone. The silane exhibited the maximum penetration, up to 24mm under favourable conditions, but penetration in all cases was limited by moisture in the substrate. Water repellent treatments slow down water vapour diffusion but, with time, internal moisture levels should reflect external relative humidities. Water repellents may be used to reduce carbonation-induced corrosion where ingress of moisture from intermittent wetting may be slowed. However, treatment with water repellents can temporarily push the carbonation front deeper into the concrete.

Ionic and molecular diffusion in cementitious materials

The work described in this thesis is an attempt to provide improved understanding of the effects of several factors affecting diffusion in hydrated cement pastes and to aid the prediction of ionic diffusion processes in cement-based materials. Effect of pore structure on diffusion was examined by means of comparative diffusion studies of quaternary ammonium ions with different ionic radii. Diffusivities of these ions in hydrated pastes of ordinary portland cement with or without addition of fly ash were determined by a quasi-steady state technique. The restriction of the pore geometry on diffusion was evaluated from the change of diffusivity in response to the change of ionic radius. The pastes were prepared at three water-cement ratios, 0.35, 0.50 and 0.65. Attempts were made to study the effect of surface charge or the electrochemical double layer at the pore/solution interface on ionic diffusion. An approach was to evaluate the zeta potentials of hydrated cement pastes through streaming potential measurements. Another approach was the comparative studies of the diffusion kinetics of chloride and dissolved oxygen in hydrated pastes of ordinary portland cement with addition of 0 and 20% fly ash. An electrochemical technique for the determination of oxygen diffusivity was also developed. Non-steady state diffusion of sodium potassium, chloride and hydroxyl ions in hydrated ordinary portland cement paste of water-cement ratio 0.5 was studied with the aid of computer-modelling. The kinetics of both diffusion and ionic binding were considered for the characterization of the concentration profiles by Fick's first and second laws. The effect of the electrostatic interactions between ions on the overall diffusion rates was also considered. A general model concerning the prediction of ionic diffusion processes in cement-based materials has been proposed.

Charge effects on hindrance factors for diffusion and convection of solute in pores I

The transport of a spherical solute through a long circular cylindrical pore filled with an electrolyte solution is studied numerically, in the presence of constant surface charge on the solute and the pore wall. Fluid dynamic analyses were carried out to calculate the flow field around the solute in the pore to evaluate the drag coefficients exerted on the solute. Electrical potentials around the solute in the electrolyte solution were computed based on a mean-field theory to provide the interaction energy between the charged solute and the pore wall. Combining the results of the fluid dynamic and electrostatic analyses, we estimated the rate of the diffusive and convective transport of the solute across the pore. Although the present estimates of the drag coefficients on the solute suggest more than 10% difference from existing studies, depending on the radius ratio of the solute relative to the pore and the radial position of the solute center in the pore, this difference leads to a minor effect on the hindrance factors. It was found that even at rather large ion concentrations, the repulsive electrostatic interaction between the charged solute and the pore wall of like charge could significantly reduce the transport rate of the solute.