The steady distribution

If the system were in equilibrium one would have c x,t)jc y,t) — f x)lf y), independently of the time t, that is, the distribution would be steady in the sense that the ratio of the populations in any two states would be independent of the time, and the steady distribution would in this case be the Boltzmann distribution. Of course, if the system were in equilibrium, then not only the ratio c x,t)lc(y,t), but also c x,t) and c y,t) separately, would be independent of the time, but the expression steady state will be used to describe the more general situation in which the population of any state may change with time, but the ratio of populations of any two states does not. 

In the second case the steady distribution of reactant molecules is the equilibrium distribution, and here the rate constant calculated from Eq. (31) and from the definition of Q x) in Eq. (30) is... 

Figure Bl.14.9. Imaging pulse sequence including flow and/or diflfiision encoding. Gradient pulses before and after the inversion pulse are supplemented in any of the spatial dimensions of the standard spin-echo imaging sequence. Motion weighting is achieved by switching a strong gradient pulse pair G, (see solid black line). The steady-state distribution of flow (coherent motion) as well as diffusion (spatially...

Figure 5,16. It is assumed that by using an exactly symmetric cone a shear rate distribution, which is very nearly uniform, within the equilibrium (i.e. steady state) flow held can be generated (Tanner, 1985). Therefore in this type of viscometry the applied torque required for the steady rotation of the cone is related to the uniform shearing stress on its surface by a simplihed theoretical equation given as...

The mathematical model most widely used for steady-state behavior of a reactor is diffusion theory, a simplification of transport theory which in turn is an adaptation of Boltzmann s kinetic theory of gases. By solving a differential equation, the flux distribution in space and time is found or the conditions on materials and geometry that give a steady-state system are determined. 

The characteristic separation curve can be deterrnined for any size separation device by sampling the feed, and coarse and fine streams during steady-state operation. A protocol for determining such selectivity functions has been pubHshed (4). This type of testing, when properly conducted, provides the relationships among d K, and a at operating conditions. These three parameters completely describe a size separation device and can be used to predict the size distribution of the fine and coarse streams. 

In any gas burner some mechanism or device (flame holder or pilot) must be provided to stabilize the flame against the flow of the unbumed mixture. This device should fix the position of the flame at the burner port. Although gas burners vary greatly in form and complexity, the distribution mechanisms in most cases are fundamentally the same. By keeping the linear velocity of a small fraction of the mixture flow equal to or less than the burning velocity, a steady flame is formed. From this pilot flame, the main flame spreads to consume the main gas flow at a much higher velocity. The area of the steady flame is related to the volumetric flow rate of the mixture by equation 18 (81,82)... 

Mechanism. The thermal cracking of hydrocarbons proceeds via a free-radical mechanism (20). Siace that discovery, many reaction schemes have been proposed for various hydrocarbon feeds (21—24). Siace radicals are neutral species with a short life, their concentrations under reaction conditions are extremely small. Therefore, the iategration of continuity equations involving radical and molecular species requires special iategration algorithms (25). An approximate method known as pseudo steady-state approximation has been used ia chemical kinetics for many years (26,27). The errors associated with various approximations ia predicting the product distribution have been given (28). 

Spin-lattice relaxation is the steady (exponential) build-up or regeneration of the Boltzmann distribution (equilibrium magnetisation) of nuelear spins in the static magnetic field. The lattice is the molecular environment of the nuclear spin with whieh energy is exchanged. 

Consider a steady unidimensional flow in a tubular reaetor as shown in Figure 8-21 in the absenee of either radial or longitudinal diffusion. The veloeity u(r) is the parabolie distribution for a Newtonian fluid at eonstant viseosity, with the fluid in the eenter of the tube spending the shortest time in the reaetor. 

Theoretical volume of distribution (Vj) of a chemical is the volume in which the chemical would be distributed if its concentration were equal to a theoretical steady-state plasma concentration (Cq) at time zero. The volume of distribution is thus obtained quite similarly as the steady state concentration of a compound in the workroom air ... 

I FIGURE 11.27 Heat conduction through an external wall. The temperature distribution over die wall thickness is linear only under steady-state conditions. 

Under steady-state conditions, the temperature distribution in the wall is only spatial and not time dependent. This is the case, e.g., if the boundary conditions on both sides of the wall are kept constant over a longer time period. The time to achieve such a steady-state condition is dependent on the thickness, conductivity, and specific heat of the material. If this time is much shorter than the change in time of the boundary conditions on the wall surface, then this is termed a quasi-steady-state condition. On the contrary, if this time is longer, the temperature distribution and the heat fluxes in the wall are not constant in time, and therefore the dynamic heat transfer must be analyzed (Fig. 11.32). 

Scandium is very widely but thinly distributed and its only rich mineral is the rare thortveitite, Sc2Si20v (p. 348), found in Norway, but since scandium has only small-scale commercial use, and can be obtained as a byproduct in the extraction of other materials, this is not a critical problem. Yttrium and lanthanum are invariably associated with lanthanide elements, the former (Y) with the heavier or Yttrium group lanthanides in minerals such as xenotime, M "P04 and gadolinite, M M SijOio (M = Fe, Be), and the latter (La) with the lighter or cerium group lanthanides in minerals such as monazite, M P04 and bastnaesite, M C03F. This association of similar metals is a reflection of their ionic radii. While La is similar in size to the early lanthanides which immediately follow it in the periodic table, Y , because of the steady fall in ionic radius along the lanthanide series (p. 1234), is more akin to the later lanthanides. 

The dependence of the in-phase and quadrature lock-in detected signals on the modulation frequency is considerably more complicated than for the case of monomolecular recombination. The steady state solution to this equation is straightforward, dN/dt = 0 Nss — fG/R, but there is not a general solution N(l) to the inhomogeneous differential equation. Furthermore, the generation rate will vary throughout the sample due to the Gaussian distribution of the pump intensity and absorption by the sample... 

One solution to the volume problem was proposed using moment analysis. The steady-state volume of distribution (Vss) can be derived from the area under the curve (AUC) and the area under the first moment curve (AUMC). 

In creeping flow with the inertia term neglected, the velocity distribution rapidly reaches a steady value after a distance of r0 inside a capillary tube. At this stage the velocity distribution showed the typical parabolic shape characteristic of a Poiseuille flow. In the case of inviscid flow where inertia is the predominant term, it takes typically (depending on the Reynolds number) a distance of 20 to 50 diameters for the flow to be fully developed (Fig. 34). With the short capillary section ( 4r0) in the present design, the velocity front remains essentially unperturbed and the velocity along the symmetry axis, i.e. vx (y = 0), is identical to v0. 

The influence of electronegative additives on the CO hydrogenation reaction corresponds mainly to a reduction in the overall catalyst activity.131 This is shown for example in Fig. 2.42 which compares the steady-state methanation activities of Ni, Co, Fe and Ru catalysts relative to their fresh, unpoisoned activities as a function of gas phase H2S concentration. The distribution of the reaction products is also affected, leading to an increase in the relative amount of higher unsaturated hydrocarbons at the expense of methane formation.6 Model kinetic studies of the effect of sulfur on the methanation reaction on Ni(lOO)132,135 and Ru(OOl)133,134 at near atmospheric pressure attribute this behavior to the inhibition effect of sulfur to the dissociative adsorption rate of hydrogen but also to the drastic decrease in the... 

Two-phase flows in micro-channels with an evaporating meniscus, which separates the liquid and vapor regions, have been considered by Khrustalev and Faghri (1996) and Peles et al. (1998, 2000). In the latter a quasi-one-dimensional model was used to analyze the thermohydrodynamic characteristics of the flow in a heated capillary, with a distinct interface. This model takes into account the multi-stage character of the process, as well as the effect of capillary, friction and gravity forces on the flow development. The theoretical and experimental studies of the steady forced flow in a micro-channel with evaporating meniscus were carried out by Peles et al. (2001). These studies revealed the effect of a number of dimensionless parameters such as the Peclet and Jacob numbers, dimensionless heat transfer flux, etc., on the velocity, temperature and pressure distributions in the liquid and vapor regions. The structure of flow in heated micro-channels is determined by a number of factors the physical properties of fluid, its velocity, heat flux on... 

Dynamic simulations for an isothermal, continuous, well-mixed tank reactor start-up were compared to experimental moments of the polymer distribution, reactant concentrations, population density distributions and media viscosity. The model devloped from steady-state data correlates with experimental, transient observations. Initially the reactor was void of initiator and polymer. 

It is seen that in the steady state the total mass is distributed between the two reservoirs in proportion to the sink coefficients (in reverse proportion to the turnover times), independent of the initial distribution. 

It should be noted that the steady-state solution of Equation (12) is not necessarily unique. This can easily be seen in the case of the four-reservoir system shown in Fig. 4-7. In the steady state all material will end up in the two accumulating reservoirs at the bottom. However, the distribution between these two reservoirs will... 

Fig. 4-7 Example of a coupled reservoir system where the steady-state distribution of mass is not uniquely determined by the parameters describing the fluxes within the system but also by the initial conditions (see text).

However, with "only" 1000 Pg emitted into the system, i.e. less than 3% of the total amount of carbon in the four reservoirs, the atmospheric reservoir would still remain significantly affected (20%) at steady state. In this case the change in oceanic carbon would be only 2% and hardly noticeable. The steady-state distributions are independent of where the addition occurs. If the CO2 from fossil fuel combustion were collected and dumped into the ocean, the final distribution would still be the same. 

Example 13.5 Determine the instantaneous distributions of chain lengths by number and weight before and after termination by combination. Apply the quasi-steady and equal reactivity assumptions to a batch polymerization with free-radical kinetics and chemical initiation. 

The time that a molecule spends in a reactive system will affect its probability of reacting and the measurement, interpretation, and modeling of residence time distributions are important aspects of chemical reaction engineering. Part of the inspiration for residence time theory came from the black box analysis techniques used by electrical engineers to study circuits. These are stimulus-response or input-output methods where a system is disturbed and its response to the disturbance is measured. The measured response, when properly interpreted, is used to predict the response of the system to other inputs. For residence time measurements, an inert tracer is injected at the inlet to the reactor, and the tracer concentration is measured at the outlet. The injection is carried out in a standardized way to allow easy interpretation of the results, which can then be used to make predictions. Predictions include the dynamic response of the system to arbitrary tracer inputs. More important, however, are the predictions of the steady-state yield of reactions in continuous-flow systems. All this can be done without opening the black box. 

The Chapman-Enskog method has been used to solve for steady state tracer diffusion (. ). According to the method the singlet distribution function for the diffusing species 1, present In a trace amount n nj, 1 1) In an otherwise equilibrium fluid. Is approximated by... 

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