Use Of Steady State Research Articles

Dynamic rate analysis for low frequency operation of chemical reactors

Periodic operation of chemical reactors can enhance reactant conversion and product selectivity. It is desirable to identify reaction kinetics and networks that may benefit from non-steady state operation and to quantify the extent of that enhancement without extensive computations. In this study, we describe a simple method to establish approximate functional dependencies of isothermal point reaction enhancement on dynamic and kinetic parameters during low frequency operation. Low frequency operation permits the use of steady state as opposed to transient conservation equations to identify limits of fractional rate enhancement. By approximating local dynamic rates as square waves modulating between two steady states, an analytical function can be derived from global rate expressions. The function relates fractional rate enhancement to concentration wave amplitudes, phase shifts, cyclic averages, duty cycles and reaction orders for one or more dynamically-fed reactants. We show that the method may be applied to predict integral conversion enhancement for ideal reactors. During integral operation, nonstoichiometric concentration waves may change phase through disproportionate consumption of reactants at wave maxima and minima, hence inverting waves out-of-phase (180°) from their initial waveform. This may cause local rate enhancement to transition to rate diminishment. Three experimental examples involving catalytic oxidations are described that illustrate selected theoretical aspects of the study.

Diffusive epidemic process in 3D: a two-species reaction–diffusion phase transition

By the use of Monte Carlo simulation we study the critical behavior of a three-dimensional stochastic lattice model describing a diffusive epidemic propagation process. In this model, healthy (A) and sick (B) individuals diffuse on the lattice with diffusion constants d A and d B , respectively, and undergo reactions B → A and A + B → 2B. We determine the absorbing phase transition between a steady reactive state and a vacuum state. We obtained the order parameter, order parameter fluctuations, correlation length and their critical exponents by the use of steady state and short-time dynamics simulations. We studied three different diffusion regimes: the case of species A diffusing much slower than species B (d A ≪ d B ), the case of species with equal diffusion constants (d A = d B ) and the case of species A diffusing much faster than species B (d A ≫ d B ). We found only second order transition for all three cases. We did not identify any signal of first order transition for the case d A > d B as predicted by field theory in first order approximation.

Changes of EEG phase synchronization and EOG signals along the use of steady state visually evoked potential-based brain computer interface

Objective. The steady-state visual evoked potential (SSVEP)-based brain computer interface (BCI) has demonstrated relatively high performance with little user training, and thus becomes a popular BCI paradigm. However, due to the performance deterioration over time, its robustness and reliability appear not sufficient to allow a non-expert to use outside laboratory. It would be thus helpful to study what happens behind the decreasing tendency of the BCI performance. Approach. This paper explores the changes of brain networks and electrooculography (EOG) signals to investigate the cognitive capability changes along the use of the SSVEP-based BCI. The EOG signals are characterized by the blink amplitudes and the speeds of saccades, and the brain networks are estimated by the instantaneous phase synchronizations of electroencephalography signals. Main results. Experimental results revealed that the characteristics derived from EOG and brain networks have similar trends which contain two stages. At the beginning, the blink amplitudes and the saccade speeds start to reduce. Meanwhile, the global synchronizations of the brain networks are formed quickly. These observations implies that the cognitive decline along the use of the SSVEP-based BCI. Then, the EOG and the brain networks related characteristics demonstrate a slow recovery or relatively stable trend. Significance. This study could be helpful for a better understanding about the depreciation of the BCI performance as well as its relationship with the brain networks and the EOG along the use of the SSVEP-based BCI.

Alpha-band lateralization during auditory selective attention for brain–computer interface control

In this paper, we investigated selective attention to auditory stimuli as a control mechanism for a Brain–Computer Interface (BCI). For BCIs using visual stimuli, the use of steady state or code modulated visual evoked potentials yields high performance. In this work, these approaches were transferred and tested in the auditory domain. The attentional modulation of code-modulated auditory evoked potentials (c-AEPs) and steady state auditory evoked potentials (SSAEPs) showed only a small effect, which is not sufficient for BCI control. However, for both kinds of stimuli, we found a spatial attention-related alpha-band lateralization that allows classification accuracies above 70% and thereby can be used for controlling a BCI.

Spectrally Resolved Resonance Energy Transfer from ZnO:MgO Nanocrystals

Resonance energy transfer (RET) from the visible emission of core−shell ZnO:MgO nanocrystals to Nile Red chromophores, following band gap excitation in the UV, has been investigated for four different nanocrystal sizes. With use of steady state and time-resolved fluorescence spectroscopic measurements the wavelength dependent RET efficiencies have been determined. The RET process in ZnO:MgO nanocrystals occurs from emissions involving trap state recombination. There are two such processes with different RET efficiencies for the same particle size. This is shown to be a consequence of the fact that the recombination processes giving rise to the two emissions are located at different distances from the center of the particle so that the donor−acceptor distances for the two are different, even for the same particle size.

An Alternate Proton Acceptor for Excited-State Proton Transfer in Green Fluorescent Protein: Rewiring GFP

The neutral form of the chromophore in wild-type green fluorescent protein (wtGFP) undergoes excited-state proton transfer (ESPT) upon excitation, resulting in characteristic green (508 nm) fluorescence. This ESPT reaction involves a proton relay from the phenol hydroxyl of the chromophore to the ionized side chain of E222, and results in formation of the anionic chromophore in a protein environment optimized for the neutral species (the I* state). Reorientation or replacement of E222, as occurs in the S65T and E222Q GFP mutants, disables the ESPT reaction and results in loss of green emission following excitation of the neutral chromophore. Previously, it has been shown that the introduction of a second mutation (H148D) into S65T GFP allows the recovery of green emission, implying that ESPT is again possible. A similar recovery of green fluorescence is also observed for the E222Q/H148D mutant, suggesting that D148 is the proton acceptor for the ESPT reaction in both double mutants. The mechanism of fluorescence emission following excitation of the neutral chromophore in S65T/H148D and E222Q/H148D has been explored through the use of steady state and ultrafast time-resolved fluorescence and vibrational spectroscopy. The data are contrasted with those of the single mutant S65T GFP. Time-resolved fluorescence studies indicate very rapid (< 1 ps) formation of I* in the double mutants, followed by vibrational cooling on the picosecond time scale. The time-resolved IR difference spectra are markedly different to those of wtGFP or its anionic mutants. In particular, no spectral signatures are apparent in the picosecond IR difference spectra that would correspond to alteration in the ionization state of D148, leading to the proposal that a low-barrier hydrogen bond (LBHB) is present between the phenol hydroxyl of the chromophore and the side chain of D148, with different potential energy surfaces for the ground and excited states. This model is consistent with recent high-resolution structural data in which the distance between the donor and acceptor oxygen atoms is < or = 2.4 A. Importantly, these studies indicate that the hydrogen-bond network in wtGFP can be replaced by a single residue, an observation which, when fully explored, will add to our understanding of the various requirements for proton-transfer reactions within proteins.

Achievement of steady state optimizes results when performing indirect calorimetry.

The use of steady state as the endpoint for performance of indirect calorimetry (IC) is controversial. We designed this prospective study to evaluate the necessity and significance of achieving steady state. Patients with respiratory failure placed on mechanical ventilation in a short- or long-term acute care unit at any 1 of 3 university-based urban hospitals were eligible for the study. The 24-hour total energy expenditure (TEE) was determined by a Nellcor Puritan Bennett 7250 continuous IC monitor. Measured gas exchange parameters were obtained and averaged every 1 minute for the initial hour and then every 15 minutes for the next 23 hours. Over the initial hour, resting energy expenditure (REE) was averaged for intervals over the first 20, 30, 40, and 60 minutes, and for various definitions of steady state where oxygen consumption (VO2) and carbon dioxide production (VCO2) changed by <10%, 15%, and 20%. Coefficient of variation (CV) was calculated for VO2 over the first 30 minutes of study. Twenty-two patients (mean age, 52.8 years, 59% male, mean Acute Physiology and Chronic Health Evaluation (APACHE III) score 42.0) were entered in the study. The best correlation between short-term "snapshot" REE and the 24-hour TEE was achieved by the steady-state period defined by the most stringent criteria (change in VO2 and VCO2 by <10%). The average REE for all steady-state and interval periods correlated significantly to TEE with no significant difference in the absolute values for REE and TEE. Adding 10% for an activity factor to the average REE for each steady-state and interval period again correlated to TEE in a similar fashion with the same R value, but the absolute values for REE + 10% for all steady-state and interval periods were significantly different than the corresponding TEE. In those patients with less variation (CV for VO2 < or = 9.0), the REE obtained for the steady-state period defined by the most stringent criteria still had the best correlation, but similar correlation could be obtained by interval testing of > or = 30-minute duration. In those patients with greater variation (CV for VO2 >9.0), interval testing of at least 60 minutes or more was required to attain levels of correlation similar to that achieved by the steady-state period defined by the most stringent criteria. These data support the use of steady state, best defined as an interval of 5 consecutive minutes whereby VO2 and VCO2 change by <10%. The mean REE from this period correlates best to the 24-hour TEE regardless of CV. IC testing can be completed after achievement of steady state. Activity factors of 10% to 15% should not be added to the steady-state REE, because this practice significantly decreases the accuracy. In patients who fail to achieve steady state, the CV helps to determine the appropriate duration of IC testing. In those patients with a low CV (< or = 9.0), 30-minute test duration is adequate. In patients with CV >9.0, test duration of at least 60 minutes may be required. These latter patients should be considered for 24-hour IC testing.

Monitoring Ternary Systems of C12E5/Water/Tetradecane via the Fluorescence of Solvatochromic Probes

In this work ternary systems of the nonionic surfactant C12E5 (C12H25(OCH2CH2)5OH), tetradecane, and water were probed by the use of steady state and time-resolved fluorescence. Microemulsions, which were rich in oil, rich in water, and also both continuous in oil and water, were monitored via the application of solvatochromic fluorescent probes. The hydrophobic laser dye Nile Red was used to report from the side of the oil−surfactant interface, while Prodan, which is soluble in each of the constituent solvents, was used to provide a global picture. To complement these, the hydrophilic dye 4-(2-(dimethylamino)phenyl)-1-methylpyridinium iodide was used to report from the side of the water−surfactant interface. The results show the partitioning of the probes into different environments within the ternary systems as evident from the solvatochromic shift in the emission spectra, uncovering similarities between the water-rich and bicontinuous regions in terms of polarity. Estimates for the polarity of the envi...

A framework for extreme-event control in wastewater treatment

In this paper an approach to extreme event control in wastewater treatment plant operation by use of automatic supervisory control is discussed. The framework presented is based on the fact that different operational conditions manifest themselves as clusters in a multivariate measurement space. These clusters are identified and linked to specific and corresponding events by use of principal component analysis and fuzzy c-means clustering. A reduced system model is assigned to each type of extreme event and used to calculate appropriate local controller set points. In earlier work we have shown that this approach is applicable to wastewater treatment control using look-up tables to determine current set points. In this work we focus on the automatic determination of appropriate set points by use of steady state and dynamic predictions. The performance of a relatively simple steady-state supervisory controller is compared with that of a model predictive supervisory controller. Also, a look-up table approach is included in the comparison, as it provides a simple and robust alternative to the steady-state and model predictive controllers. The methodology is illustrated in a simulation study.

Modelling intercompartment transfer of pollutants: The case of lead

The concentrations of pollutants in different environmental compartments (air, water, sediment, soil) are related to each other through the action of intercompartment mass transfer processes. The influence of such intercompartment mass transfer processes (air-soil and air-water exchange, soil-groundwater transfer, water-sediment exchange, etc.) on the fate of pollutants in the environment is generally very considerable, not only for organic substances, but perhaps even more so for heavy metals. The extent of the mutual influence of concentrations in specific environmental situations can be successfully evaluated by means of multimedia box models of the type originally proposed by Mackay and co-workers, provided that the rates of intercompartment mass transfer processes are adequately described. The use of steady state and quasi-dynamic multimedia box models as diagnostic tools in evaluating the intercompartment dependence of the concentrations of lead is illustrated by two hypothetical environmental situations. It is suggested that future legislation to control pollution in one compartment should consider its effect on the other environmental compartments, and that attempts should be made to incorporate multimedia modelling in procedures to derive environmental quality standards.

Computer-aided design and control of an activated sludge process

The activated sludge process for wastewater treatment is studied by use of steady state and dynamic process models. Process constraints fix the steady The transient analysis enables controllability to be taken into account when making a final design decision between alternatives that are equally attra

On the Scaling of Impulsively Started Incompressible Turbulent Round Jets

A scaling law for transient, turbulent, incompressible, round jets is reported. Numerical solutions of the Navier-Stokes equations were obtained using a k-ε model for turbulence. The constants of the k-ε model were optimized by comparing computed centerline velocity, mean radial velocity distribution, longitudinal kinetic energy distributions with those measured by other authors in steady round jets. The resulting constants are those also used in computations of steady planar jets except for the one that multiplies the source term in the ε-equation. After optimization, the agreement is satisfactory for all mean quantities but is still rather poor for the kinetic energy distribution. Parameteric studies of the transient were performed for 9•103 ≤ ReD ≤ 105. Then the definition was adopted that a jet reaches steady state between the nozzle and an axial location when, at that location, the centerline velocity achieves 70 percent of its steady state value, and characteristic steadying length and time scales (D•ReD0.053 and D•ReD0.053/u cL,0 respectively) were determined as well as a unique function that relates dimensionless steadying time to dimensionless steadying length. This function changes in a predictable way if a percent other than 70 is selected but the characteristic length and time scales do not. It is found that the 70 percent threshold is reached within the head vortex of the transient jet. Thus a transient jet, practically, is a steady jet except within its head vortex. This, in part, justifies our use of steady state k-ε constants in our transient computations. The computed jet tip arrival times are shown to compare favorably with measured ones.

The electrodissolution and passivation of mild steel in alkaline sulphide solutions

The electrodissolution and passivation of mild steel in alkaline sulphide solutions at 25°C is investigated by the use of steady state and transient electrochemical techniques and by scanning electron microscopy and energy dispersive X-ray analysis. The electrodissolution and passivation processes are explained by the initial competitive adsorption of OH −, HS − and H 2O and the subsequent charge transfer and proton transfer processes involving the OH and HS adsorbed species. The former is responsible for the passivation of the metal by an oxide metal layer while the second species undergoes two different reactions yielding in one case a precipitated mackinawite film on the metal, which is a poorly protective layer, and in the other a soluble Fe(II) species which can be detected by chemical analysis. The contribution of the reactions starting from each adsorbed species depends on the HS −/OH − concentration ratio in the solution. The initiation of pitting on iron is also explained through the postulated reaction pattern.