For the steady-state case, Z should also give the forward rate of formation or flux of critical nuclei, except that the positive free energy of their formation amounts to a free energy of activation. If one correspondingly modifies the rate Z by the term an approximate value for I results [Pg.331]

Derive the steady-state rate law corresponding to the reaction sequence of Eqs. XVIII-40-XVIII-44, that is, without making the assumption that any one step is much slower than the others. See Ref 234. [Pg.741]

Fig. rV-26. Steady-state diffusion model for film dissolution. (From Ref. 293.) [Pg.150]

Figure A3.1.4. Steady state heat eonduetion, illustrating the flow of energy aeross a plane at a height z. |

Thus, this eigenvalue detenuines the unimolecular steady-state reaction rate constant. [Pg.1051]

Kirkpatrick T R, Cohen E G D and Dorfman J R 1982 Light scattering by a fluid in a nonequilibrium steady state. II. Large gradients Phys. Rev. A 26 995 [Pg.715]

There are tliree steps in the calculation first, solve the frill nonlinear set of hydrodynamic equations in the steady state, where the time derivatives of all quantities are zero second, linearize about the steady-state solutions third, postulate a non-equilibrium ensemble through a generalized fluctuation dissipation relation. [Pg.728]

Another possibility is that a system may be held in a constrained equilibrium by external forces and thus be in a non-equilibrium steady state (NESS). In this case, the spatio-temporal correlations contain new ingredients, which are also exemplified in section A3.3.2. [Pg.716]

In both preceding cases, the demands to the electrolysis unit are limited, since there is no need to keep the silver content in the fixer tank constantly low. A steady state silver concentration in the fixer between 3 and 5 g/1 is acceptable, since this causes no substantial loss of fixation speed. [Pg.605]

A] = b/a (equation (A3.4.145)) is stationary and not [A ] itself This suggests d[A ]/dt < d[A]/dt as a more appropriate fomuilation of quasi-stationarity. Furthemiore, the general stationary state solution (equation (A3.4.144)) for the Lindemaim mechanism contams cases that are not usually retained in the Bodenstein quasi-steady-state solution. [Pg.791]

Rate laws have also been observed that correspond to there being two kinds of surface, one adsorbing reactant A and the other reactant B and with the rate proportional to 5a x 5b- For traditional discussions of Langmuir-Hinshelwood rate laws, see Refs. 240-242. Many catalytic systems involve a series of intermediates, and the simplifying assumption of steady-state equilibrium is usually made. See Boudart and co-workers [243-245] for a contemporary discussion of such complexities. [Pg.728]

General first-order kinetics also play an important role for the so-called local eigenvalue analysis of more complicated reaction mechanisms, which are usually described by nonlinear systems of differential equations. Linearization leads to effective general first-order kinetics whose analysis reveals infomiation on the time scales of chemical reactions, species in steady states (quasi-stationarity), or partial equilibria (quasi-equilibrium) [M, and ]. [Pg.791]

The basic assumption is that the Langmuir equation applies to each layer, with the added postulate that for the first layer the heat of adsorption Q may have some special value, whereas for all succeeding layers, it is equal to Qu, the heat of condensation of the liquid adsorbate. A furfter assumption is that evaporation and condensation can occur only from or on exposed surfaces. As illustrated in Fig. XVII-9, the picture is one of portions of uncovered surface 5o, of surface covered by a single layer 5, by a double-layer 52. and so on.f The condition for equilibrium is taken to be that the amount of each type of surface reaches a steady-state value with respect to the next-deeper one. Thus for 5o [Pg.619]

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