Hysteresis and phase transitions in a single partially internally wetted catalyst pellet: Thermogravimetric studies

The hydrogenation of cyclohexene over palladium supported in a microporous gamma-alumina pellet is studied thermogravimetrically with a view to measuring the extent of partial internal wetting associated with the different steady state branches. As many as three steady state branches having significantly different degrees of internal wetting and reaction rates, with transitions between them, are confirmed from observations of catalyst weight change. It is seen that with reduction in catalyst activity the middle branch, obtained by condensation from a vapor filled pellet, is much more prominent without showing an evaporative transition for the range of hydrogen partial pressures used here. The catalyst activity is therefore an important parameter affecting the structure of the steady state branches. Hysteresis effects are found to occur, and the thermogravimetric results also confirm the importance of history in determining the catalyst state. The measured degree of wetting is in accordance with that estimated from a mathematical model incorporating capillary condensation effects in addition to reaction-diffusion phenomena. The same model also satisfactorily interprets the reaction rate variations and transitions seen in the present work.

Experimental and theoretical investigations of adsorption hysteresis and criticality in MCM-41: Studies with O-2, Ar, and CO2

MCM-41 materials of six different pore diameters were prepared and characterized using X-ray diffraction, transmission electron microscopy, helium pycnometry, small-angle neutron scattering, and gas adsorption (argon at 77.4 and 87.4 K, nitrogen and oxygen at 77.4 K, and carbon dioxide at 194.6 K). A recent molecular continuum model of the authors, previously used for adsorption of nitrogen at 77.4 K, was applied here for adsorption of argon, oxygen, and carbon dioxide. While model predictions of single-pore adsorption isotherms for argon and oxygen are in satisfactory agreement with experimental data, significant deviation was found for carbon dioxide, most likely due to its high quadrupole moment. Predictions of critical pore diameter, below which reversible condensation occurs: were possible by the model and found to be consistent with experimental estimates, for the adsorption of the various gases. On the other hand, existing models such as the Barrett-Joyner-Halenda (BJH), Saito-Foley, and Dubinin-Astakhov models were found to be inadequate, either predicting an incorrect pore diameter or not correlating the isotherms adequately. The wall structure of MCM-41 appears to be close to that of amorphous silica, as inferred from our skeletal density measurements.

Adsorption hysteresis and criticality in regular mesoporous materials

In the present work, various theories predicting the critical diameter for the absence of capillary condensation and hysteresis are applied to experimental adsorption isotherms of vapors on regular mesoporous materials. Among the various theories studied, the tensile strength approximation proposed by the authors was found to be the most successful. Reversibility of nitrogen adsorption at 77.4 K was studied on pure MCM-41 of various pore sizes, as well as mixtures of pure MCM-41 samples in a 1:1 ratio. The results of PSD and hysteresis on MCM-41 mixtures are close to that expected from studies of the pure materials. The estimates of hysteresis critical temperature and diameter of MCM-41, HMS, FSM and KIT materials are also provided.

The effect of heat transfer mode on heart rate responses and hysteresis during heating and cooling in the estuarine crocodile Crocodylus porosus

The effect of heating and cooling on heart rate in the estuarine crocodile Crocodylus porosus was studied in response to different heat transfer mechanisms and heat loads. Three heating treatments were investigated. C. porosus were: (1) exposed to a radiant heat source under dry conditions; (2) heated via radiant energy while half-submerged in flowing water at 23degreesC and (3) heated via convective transfer by increasing water temperature from 23degreesC to 35degreesC. Cooling was achieved in all treatments by removing the heat source and with C. porosus half-submerged in flowing water at 23degreesC. In all treatments, the heart rate of C. porosus increased markedly in response to heating and decreased rapidly with the removal of the heat source. Heart rate during heating was significantly faster than during cooling at any given body temperature, i.e. there was a significant heart rate hysteresis. There were two identifiable responses to heating and cooling. During the initial stages of applying or removing the heat source, there was a dramatic increase or decrease in heart rate ('rapid response'), respectively, indicating a possible cardiac reflex. This rapid change in heart rate with only a small change or no change in body temperature (

Influence of hysteresis on tidal capillary fringe dynamics in a well-sorted sand

Nielsen and Perrochet [Adv. Water Resour. 23 (2000) 503] presented experimental data for cyclic water movement in the vadose zone above an oscillating watertable. The response of the watertable to cyclic forcing was characterised by the ratios of the forcing head to watertable amplitudes and their associated phase lag. They found that their non-hysteretic Richards' equation model failed to represent the observed behaviour of these parameters. This paper explores the effect on the simulated capillary fringe dynamics (in terms of these parameters) of including varying degrees of hysteresis in the moisture retention curve used in a numerical model of their experiment. It is clear that hysteresis can indeed account for observed discrepancies between simulation and experiment and that the effect of hysteresis varies with the frequency of oscillation. The use of a single-valued mean retention curve, as advocated by some authors, fails to provide a match between the simulated and observed behaviour of the Nielsen and Perrochet parameters, but is shown to be adequate for predicting time-averaged soil moisture profiles. (C) 2003 Elsevier Ltd. All rights reserved.

A cold model study of raceway hysteresis

The effect of a gas flow field on the size of raceway has been studied experimentally using a two-dimensional (2-D) cold model. It is observed that as the blast velocity from the tuyere increases, raceway size increases, and when the blast velocity is decreased from its highest value, raceway size does not change much until the velocity reaches a critical velocity. Below the critical velocity, raceway size decreases with decreasing velocity but is always larger than that for the same velocity when the velocity increased. This phenomenon is called raceway hysteresis. Raceway hysteresis has been studied in the presence of different gas flow rates and different particle densities. Raceway hysteresis has been observed in all the experiments. The effect of liquid flow, with various superficial velocities, on raceway hysteresis has also been studied. A study of raceway size hysteresis shows that interparticle and particle-wall friction have a very large effect on raceway size. A hypothesis has been proposed to describe the hysteresis phenomenon in the packed beds. The relevance of hysteresis to blast furnace raceways has been discussed. Existing literature correlations for raceway size ignore the frictional effects. Therefore, their applicability to the ironmaking blast furnace is questionable.

Physiological thermoregulation in a crustacean? Heart rate hysteresis in the freshwater crayfish Cherax destructor

Differential heart rates during heating and cooling (heart rate hysteresis) are an important thermoregulatory mechanism in ectothermic reptiles. We speculate that heart rate hysteresis has evolved alongside vascularisation, and to determine whether this phenomenon occurs in a lineage with vascularised circulatory systems that is phylogenetically distant from reptiles, we measured the response of heart rate to convective heat transfer in the Australian freshwater crayfish, Cherax destructor. Heart rate during convective heating (from 20 to 30 degreesC) was significantly faster than during cooling for any given body temperature. Heart rate declined rapidly immediately following the removal of the heat source, despite only negligible losses in body temperature. This heart rate 'hysteresis' is similar to the pattern reported in many reptiles and, by varying peripheral blood flow, it is presumed to confer thermoregulatory benefits particularly given the thermal sensitivity of many physiological rate functions in crustaceans. (C) 2004 Published by Elsevier Inc.

Local liquid holdups and hysteresis in a 2-D packed bed using X-ray radiography

An X-ray visualization technique has been used for the quantitative determination of local liquid holdups distribution and liquid holdup hysteresis in a nonwetting two-dimensional (2-D) packed bed. A medical diagnostic X-ray unit has been used to image the local holdups in a 2-D cold model having a random packing of expanded polystyrene beads. An aqueous barium chloride solution was used as a fluid to achieve good contrast on X-ray images. To quantify the local liquid holdup, a simple calibration technique has been developed that can be used for most of the radiological methods such as gamma ray and neutron radiography. The global value of total liquid holdup, obtained by X-ray method, has been compared with two conventional methods: drainage and tracer response. The X-ray technique, after validation, has been used to visualize and quantify, the liquid hysteresis phenomena in a packed bed. The liquid flows in preferred paths or channels that carry droplets/rivulets of increasing size and number as the liquid flow rate is increased. When the flow is reduced, these paths are retained and the higher liquid holdup that persists in these regions leads to the holdup hysteresis effect. Holdup in some regions of the packed bed may be an order of magnitude higher than average at a particular flow rate. (c) 2005 American Institute of Chemical Engineers

Mechanics of raceway hysteresis in a packed bed

When a gas is introduced at high velocity through a nozzle into a packed bed, it creates a raceway in the packed bed. It has been found that the raceway size is larger when it is formed by decreasing the gas velocity from its highest value than when it is formed by increasing the gas velocity. This phenomenon is known as raceway hysteresis. A hypothesis has been oroposed to explain the hysteresis phenomenon based on a force-balance approach which includes frictional, bed-weight, and pressure forces. According to this hypothesis, the frictional force acts in different directions when the raceway is expanding and contracting. In this article, the entire packed bed has been divided into radial and Cartesian co-ordinate systems, and the forces acting on the raceway have been solved analytically for a simplified one-dimensional case. Based on the force-balance approach, a general equation has been obtained to predict the diameter of the raceway for increasing And decreasing velocities. A reasonable agreement has been found between the theoretical predictions and experimental observations. The model has also been compared with published experimental and plant data. The hysteresis mechanism in the packed beds can be described reasonably by taking into consideration the direction of frictional forces for the increasing- and decreasin-velocity cases. The effects of the particleshape factor and void fraction on the raceway hysteresis are examined.

Artificial pumping errors in the Kool-Parker scaling model of soil moisture hysteresis

Hysteresis models that eliminate the artificial pumping errors associated with the Kool-Parker (KP) soil moisture hysteresis model, such as the Parker-Lenhard (PL) method, can be computationally demanding in unsaturated transport models since they need to retain the wetting-drying history of the system. The pumping errors in these models need to be eliminated for correct simulation of cyclical systems (e.g. transport above a tidally forced watertable, infiltration and redistribution under periodic irrigation) if the soils exhibit significant hysteresis. A modification is made here to the PL method that allows it to be more readily applied to numerical models by eliminating the need to store a large number of soil moisture reversal points. The modified-PL method largely eliminates any artificial pumping error and so essentially retains the accuracy of the original PL approach. The modified-PL method is implemented in HYDRUS-1D (version 2.0), which is then used to simulate cyclic capillary fringe dynamics to show the influence of removing artificial pumping errors and to demonstrate the ease of implementation. Artificial pumping errors are shown to be significant for the soils and system characteristics used here in numerical experiments of transport above a fluctuating watertable. (c) 2005 Elsevier B.V. All rights reserved.

Adsorption in mesopores: A molecular-continuum model with application to MCM-41

The classical model of surface layering followed by capillary condensation during adsorption in mesopores, is modified here by consideration of the adsorbate solid interaction potential. The new theory accurately predicts the capillary coexistence curve as well as pore criticality, matching that predicted by density functional theory. The model also satisfactorily predicts the isotherm for nitrogen adsorption at 77.4 K on MCM-41 material of various pore sizes, synthesized and characterized in our laboratory, including the multilayer region, using only data on the variation of condensation pressures with pore diameter. The results indicate a minimum mesopore diameter for the surface layering model to hold as 14.1 Å, below which size micropore filling must occur, and a minimum pore diameter for mechanical stability of the hemispherical meniscus during desorption as 34.2 Å. For pores in-between these two sizes reversible condensation is predicted to occur, in accord with the experimental data for nitrogen adsorption on MCM-41 at 77.4 K.

Spontaneous transitions in the coordination of a whole body task

This paper describes an example of spontaneous transitions between qualitatively different coordination patterns during a cyclic lifting and lowering task. Eleven participants performed 12 trials of repetitive lifting and lowering in a ramp protocol in which the height of the lower shelf was raised or lowered 1 cm per cycle between 10 and 50 cm. Two distinct patterns of coordination were evident: a squat technique in which moderate range of hip, knee and ankle movement was utilised and ankle plantar-flexion occurred simultaneously with knee and hip extension; and a stoop technique in which the range of knee movement was reduced and knee and hip extension was accompanied by simultaneous ankle dorsi-flexion. Abrupt transitions from stoop to squat techniques were observed during descending trials, and from squat to stoop during ascending trials. Indications of hysteresis was observed in that transitions were more frequently observed during descending trials, and the average shelf height at the transition was 5 cm higher during ascending trials. The transitions may be a consequence of a trade-off between the biomechanical advantages of each technique and the influence of the lift height on this trade-off.

A model for adsorption of condensable vapors on nonporous materials

A new isotherm is proposed here for adsorption of condensable vapors and gases on nonporous materials having type II isotherms according to the Brunauer-Deming-Deming-Teller (BDDH) classification. The isotherm combines the recent molecular-continuum model in the multilayer region, with other widely used models for sub-monolayer coverage, some of which satisfy the requirement of a Henry's law asymptote. The model is successfully tested using isotherm data for nitrogen adsorption on nonporous silica, carbon and alumina, as well as benzene and hexane adsorption on nonporous carbon. Based on the data fits, out of several different alternative choices of model for the monolayer region, the Freundlich and the Unilan models are found to be the most successful when combined with the multilayer model to predict the whole isotherm. The hybrid model is consequently applicable over a wide pressure range. (C) 2000 Elsevier Science B.V. All rights reserved.

Comprehensive structural characterization of MCM-41: From mesopores to particles

In the present work the meso- and macro-structural characteristics of the mesoporous adsorbent MCM-41 have been estimated with the help of various techniques. The structure is found to comprise four different length scales: that of the mesopores, the crystallites, the grains and of the particles. It was found that the surface area estimated by the use of small angle scattering techniques is higher, while that estimated by mercury porosimetry is much lower, than that obtained from gas adsorption methods. Based on the macropore characterization by mercury porosimetry, and the considerable macropore area determined, it is seen that the actual mesopore area of MCM-41 may be significantly lower than the BET area. TEM studies indicated that MCM-41 does not have an ideal mesopore structure; however, it may still be treated as a model mesoporous material for gas adsorption studies because of the large radius of curvature of the channels.

Kinetics of photoacclimation in corals

Traditional models describing the relationship between photosynthesis (P) and irradiance (I) do not account for photoacclimation to short-term variation in irradiance. Here we develop and test a model that predicts the rate of photosynthesis under fluctuating irradiances at the scale of days to weeks. Using oxygen respirometry, we measured the rates of change in the P-I model parameters P-max (maximum rate of gross photosynthesis) and I-k (sub-saturation irradiance) of the photo-symbiotic coral Turbinaria mesenterina (Lamarck) following large and small increases and decreases in growth irradiance. We analyse the behaviour of the dynamic P-I model in turbid-water conditions using a dataset of 3-month continuous irradiance as the input variable. In response to upward or downward changes in experimental growth irradiance, I-k values decreased or increased exponentially, reaching new and stable levels within 5-10 days. I-k responded 4 times stronger than P-max to changes in growth irradiance. The kinetics of I-k did not show hysteresis, and changed in similar ways when irradiance was increased or decreased in small or large amounts. This suggests that mechanisms associated with photo-protection during increases in irradiance, and the maximisation of photosynthetic efficiency during decreases in irradiance, are equally potent. On the scale of months, the dynamic P-I model did not predict higher rates of photosynthesis than the static P-I model, but buffered the variation in photosynthesis during periods of reduced irradiance. Fourier analysis indicated that the kinetics of I-k closely matches the main periodicities in daily irradiance (1-2 weeks). The recorded kinetics of photoacclimation in the Turbinaria-zooxanthella symbiosis is comparable to that of free-living phytoplankton and faster than that of higher plants.