A mathematical approach to chemical equilibrium theory for gaseous systems—II: extensions and applications

Straightforward mathematical techniques are used innovatively to form a coherent theoretical system to deal with chemical equilibrium problems. For a systematic theory it is necessary to establish a system to connect different concepts. This paper shows the usefulness and consistence of the system by applications of the theorems introduced previously. Some theorems are shown somewhat unexpectedly to be mathematically correlated and relationships are obtained in a coherent manner. It has been shown that theorem 1 plays an important part in interconnecting most of the theorems. The usefulness of theorem 2 is illustrated by proving it to be consistent with theorem 3. A set of uniform mathematical expressions are associated with theorem 3. A variety of mathematical techniques based on theorems 1–3 are shown to establish the direction of equilibrium shift. The equilibrium properties expressed in initial and equilibrium conditions are shown to be connected via theorem 5. Theorem 6 is connected with theorem 4 through the mathematical representation of theorem 1.

On the solvability of second kind integral equations on the real line

This paper considers general second kind integral equations of the form(in operator form φ − kφ = ψ), where the functions k and ψ are assumed known, with ψ ∈ Y, the space of bounded continuous functions on R, and k such that the mapping s → k(s, · ), from R to L1(R), is bounded and continuous. The function φ ∈ Y is the solution to be determined. Conditions on a set W ⊂ BC(R, L1(R)) are obtained such that a generalised Fredholm alternative holds: If W satisfies these conditions and I − k is injective for all k ∈ W then I − k is also surjective for all k ∈ W and, moreover, the inverse operators (I − k) − 1 on Y are uniformly bounded for k ∈ W. The approximation of the kernel in the integral equation by a sequence (kn) converging in a weak sense to k is also considered and results on stability and convergence are obtained. These general theorems are used to establish results for two special classes of kernels: k(s, t) = κ(s − t)z(t) and k(s, t) = κ(s − t)λ(s − t, t), where κ ∈ L1(R), z ∈ L∞(R), and λ ∈ BC((R\{0}) × R). Kernels of both classes arise in problems of time harmonic wave scattering by unbounded surfaces. The general integral equation results are here applied to prove the existence of a solution for a boundary integral equation formulation of scattering by an infinite rough surface and to consider the stability and convergence of approximation of the rough surface problem by a sequence of diffraction grating problems of increasingly large period.

On the solvability of a class of second kind integral equations on unbounded domains

We consider integral equations of the form ψ(x) = φ(x) + ∫Ωk(x, y)z(y)ψ(y) dy(in operator form ψ = φ + Kzψ), where Ω is some subset ofRn(n ≥ 1). The functionsk,z, and φ are assumed known, withz ∈ L∞(Ω) and φ ∈ Y, the space of bounded continuous functions on Ω. The function ψ ∈ Yis to be determined. The class of domains Ω and kernelskconsidered includes the case Ω = Rnandk(x, y) = κ(x − y) with κ ∈ L1(Rn), in which case, ifzis the characteristic function of some setG, the integral equation is one of Wiener–Hopf type. The main theorems, proved using arguments derived from collectively compact operator theory, are conditions on a setW ⊂ L∞(Ω) which ensure that ifI − Kzis injective for allz ∈ WthenI − Kzis also surjective and, moreover, the inverse operators (I − Kz)−1onYare bounded uniformly inz. These general theorems are used to recover classical results on Wiener–Hopf integral operators of21and19, and generalisations of these results, and are applied to analyse the Lippmann–Schwinger integral equation.

Changes in storm track and cyclone activity in three SRES ensemble experiments with the ECHAM5/MPI-OM1 GCM

Synoptic activity over the Northern Hemisphere is evaluated in ensembles of ECHAM5/MPI-OM1 simulations for recent climate conditions (20C) and for three climate scenarios (following SRES A1B, A2, B1). A close agreement is found between the simulations for present day climate and the respective results from reanalysis. Significant changes in the winter mid-tropospheric storm tracks are detected in all three scenario simulations. Ensemble mean climate signals are rather similar, with particularly large activity increases downstream of the Atlantic storm track over Western Europe. The magnitude of this signal is largely dependent on the imposed change in forcing. However, differences between individual ensemble members may be large. With respect to the surface cyclones, the scenario runs produce a reduction in cyclonic track density over the mid-latitudes, even in the areas with increasing mid-tropospheric activity. The largest decrease in track densities occurs at subtropical latitudes, e.g., over the Mediterranean Basin. An increase of cyclone intensities is detected for limited areas (e.g., near Great Britain and Aleutian Isles) for the A1B and A2 experiments. The changes in synoptic activity are associated with alterations of the Northern Hemisphere circulation and background conditions (blocking frequencies, jet stream). The North Atlantic Oscillation index also shows increased values with enhanced forcing. With respect to the effects of changing synoptic activity, the regional change in cyclone intensities is accompanied by alterations of the extreme surface winds, with increasing values over Great Britain, North and Baltic Seas, as well as the areas with vanishing sea ice, and decreases over much of the subtropics.

On the existence of two-dimensional Euler flows satisfying energy-Casimir stability criteria

The energy-Casimir stability method, also known as the Arnold stability method, has been widely used in fluid dynamical applications to derive sufficient conditions for nonlinear stability. The most commonly studied system is two-dimensional Euler flow. It is shown that the set of two-dimensional Euler flows satisfying the energy-Casimir stability criteria is empty for two important cases: (i) domains having the topology of the sphere, and (ii) simply-connected bounded domains with zero net vorticity. The results apply to both the first and the second of Arnold’s stability theorems. In the spirit of Andrews’ theorem, this puts a further limitation on the applicability of the method. © 2000 American Institute of Physics.

Averaging, slaving and balance dynamics in a simple atmospheric model

We report numerical results from a study of balance dynamics using a simple model of atmospheric motion that is designed to help address the question of why balance dynamics is so stable. The non-autonomous Hamiltonian model has a chaotic slow degree of freedom (representing vortical modes) coupled to one or two linear fast oscillators (representing inertia-gravity waves). The system is said to be balanced when the fast and slow degrees of freedom are separated. We find adiabatic invariants that drift slowly in time. This drift is consistent with a random-walk behaviour at a speed which qualitatively scales, even for modest time scale separations, as the upper bound given by Neishtadt’s and Nekhoroshev’s theorems. Moreover, a similar type of scaling is observed for solutions obtained using a singular perturbation (‘slaving’) technique in resonant cases where Nekhoroshev’s theorem does not apply. We present evidence that the smaller Lyapunov exponents of the system scale exponentially as well. The results suggest that the observed stability of nearly-slow motion is a consequence of the approximate adiabatic invariance of the fast motion.

A Hamiltonian weak-wave model for shallow-water flow

A reduced dynamical model is derived which describes the interaction of weak inertia–gravity waves with nonlinear vortical motion in the context of rotating shallow–water flow. The formal scaling assumptions are (i) that there is a separation in timescales between the vortical motion and the inertia–gravity waves, and (ii) that the divergence is weak compared to the vorticity. The model is Hamiltonian, and possesses conservation laws analogous to those in the shallow–water equations. Unlike the shallow–water equations, the energy invariant is quadratic. Nonlinear stability theorems are derived for this system, and its linear eigenvalue properties are investigated in the context of some simple basic flows.

Nonlinear stability of continuously stratified quasi-geostrophic flow

Nonlinear stability theorems analogous to Arnol'd's second stability theorem are established for continuously stratified quasi-geostrophic flow with general nonlinear boundary conditions in a vertically and horizontally confined domain. Both the standard quasi-geostrophic model and the modified quasi-geostrophic model (incorporating effects of hydrostatic compressibility) are treated. The results establish explicit upper bounds on the disturbance energy, the disturbance potential enstrophy, and the disturbance available potential energy on the horizontal boundaries, in terms of the initial disturbance fields. Nonlinear stability in the sense of Liapunov is also established.

Nonlinear stability of multilayer quasi-geostrophic flow

New nonlinear stability theorems are derived for disturbances to steady basic flows in the context of the multilayer quasi-geostrophic equations. These theorems are analogues of Arnol’d's second stability theorem, the latter applying to the two-dimensional Euler equations. Explicit upper bounds are obtained on both the disturbance energy and disturbance potential enstrophy in terms of the initial disturbance fields. An important feature of the present analysis is that the disturbances are allowed to have non-zero circulation. While Arnol’d's stability method relies on the energy–Casimir invariant being sign-definite, the new criteria can be applied to cases where it is sign-indefinite because of the disturbance circulations. A version of Andrews’ theorem is established for this problem, and uniform potential vorticity flow is shown to be nonlinearly stable. The special case of two-layer flow is treated in detail, with particular attention paid to the Phillips model of baroclinic instability. It is found that the short-wave portion of the marginal stability curve found in linear theory is precisely captured by the new nonlinear stability criteria.

Rigorous bounds on the nonlinear saturation of instabilities to parallel shear flows

A novel method is presented for obtaining rigorous upper bounds on the finite-amplitude growth of instabilities to parallel shear flows on the beta-plane. The method relies on the existence of finite-amplitude Liapunov (normed) stability theorems, due to Arnol'd, which are nonlinear generalizations of the classical stability theorems of Rayleigh and Fjørtoft. Briefly, the idea is to use the finite-amplitude stability theorems to constrain the evolution of unstable flows in terms of their proximity to a stable flow. Two classes of general bounds are derived, and various examples are considered. It is also shown that, for a certain kind of forced-dissipative problem with dissipation proportional to vorticity, the finite-amplitude stability theorems (which were originally derived for inviscid, unforced flow) remain valid (though they are no longer strictly Liapunov); the saturation bounds therefore continue to hold under these conditions.

Nonlinear stability and the saturation of instabilities to axisymmetric vortices

Nonlinear stability theorems are presented for axisymmetric vortices under the restriction that the disturbance is independent of either the azimuthal or the axial coordinate. These stability theorems are then used, in both cases, to derive rigorous upper bounds on the saturation amplitudes of instabilities. Explicit examples of such bounds are worked out for some canonical profiles. The results establish a minimum order for the dependence of saturation amplitude on supercriticality, and are thereby suggestive as to the nature of the bifurcation at the stability threshold.

On the interpretation of Andrews’ theorem

Andrews (1984) has shown that any flow satisfying Arnol'd's (1965, 1966) sufficient conditions for stability must be zonally-symmetric if the boundary conditions on the flow are zonally-symmetric. This result appears to place very strong restrictions on the kinds of flows that can be proved to be stable by Arnol'd's theorems. In this paper, Andrews’ theorem is re-examined, paying special attention to the case of an unbounded domain. It is shown that, in that case, Andrews’ theorem generally fails to apply, and Arnol'd-stable flows do exist that are not zonally-symmetric. The example of a circular vortex with a monotonic vorticity profile is a case in point. A proof of the finite-amplitude version of the Rayleigh stability theorem for circular vortices is also established; despite its similarity to the Arnol'd theorems it seems not to have been put on record before.

Non-ergodicity of inviscid two-dimensional flow on a beta-plane and on the surface of a rotating sphere

It is shown that, for a sufficiently large value of β, two-dimensional flow on a doubly-periodic beta-plane cannot be ergodic (phase-space filling) on the phase-space surface of constant energy and enstrophy. A corresponding result holds for flow on the surface of a rotating sphere, for a sufficiently rapid rotation rate Ω. This implies that the higher-order, non-quadratic invariants are exerting a significant influence on the statistical evolution of the flow. The proof relies on the existence of a finite-amplitude Liapunov stability theorem for zonally symmetric basic states with a non-vanishing absolute-vorticity gradient. When the domain size is much larger than the size of a typical eddy, then a sufficient condition for non-ergodicity is that the wave steepness ε < 1, where ε = 2[surd radical]2Z/βU in the planar case and $\epsilon = 2^{\frac{1}{4}} a^{\frac{5}{2}}Z^{\frac{7}{4}}/\Omega U^{\frac{5}{2}}$ in the spherical case, and where Z is the enstrophy, U the r.m.s. velocity, and a the radius of the sphere. This result may help to explain why numerical simulations of unforced beta-plane turbulence (in which ε decreases in time) seem to evolve into a non-ergodic regime at large scales.

Sea ice–ocean coupling using a rescaled vertical coordinate z*

Realistic representation of sea ice in ocean models involves the use of a non-linear free-surface, a real freshwater flux and observance of requisite conservation laws. We show here that these properties can be achieved in practice through use of a rescaled vertical coordinate ‘‘z*” in z-coordinate models that allows one to follow undulations in the free-surface under sea ice loading. In particular, the adoption of "z*" avoids the difficult issue of vanishing levels under thick ice. Details of the implementation within MITgcm are provided. A high resolution global ocean sea ice simulation illustrates the robustness of the z* formulation and reveals a source of oceanic variability associated with sea ice dynamics and ice-loading effects. The use of the z* coordinate allows one to achieve perfect conservation of fresh water, heat and salt, as shown in extended integration of coupled ocean sea ice atmospheric model.

Scene understanding for auto-calibration of surveillance cameras

In the last decade, several research results have presented formulations for the auto-calibration problem. Most of these have relied on the evaluation of vanishing points to extract the camera parameters. Normally vanishing points are evaluated using pedestrians or the Manhattan World assumption i.e. it is assumed that the scene is necessarily composed of orthogonal planar surfaces. In this work, we present a robust framework for auto-calibration, with improved results and generalisability for real-life situations. This framework is capable of handling problems such as occlusions and the presence of unexpected objects in the scene. In our tests, we compare our formulation with the state-of-the-art in auto-calibration using pedestrians and Manhattan World-based assumptions. This paper reports on the experiments conducted using publicly available datasets; the results have shown that our formulation represents an improvement over the state-of-the-art.