How does the Earth system generate and maintain thermodynamic disequilibrium and what does it imply for the future of the planet?

The Earth's chemical composition far from chemical equilibrium is unique in our Solar System, and this uniqueness has been attributed to the presence of widespread life on the planet. Here, I show how this notion can be quantified using non-equilibrium thermodynamics. Generating and maintaining disequilibrium in a thermodynamic variable requires the extraction of power from another thermodynamic gradient, and the second law of thermodynamics imposes fundamental limits on how much power can be extracted. With this approach and associated limits, I show that the ability of abiotic processes to generate geochemical free energy that can be used to transform the surface–atmosphere environment is strongly limited to less than 1 TW. Photosynthetic life generates more than 200 TW by performing photochemistry, thereby substantiating the notion that a geochemical composition far from equilibrium can be a sign for strong biotic activity. Present-day free energy consumption by human activity in the form of industrial activity and human appropriated net primary productivity is of the order of 50 TW and therefore constitutes a considerable term in the free energy budget of the planet. When aiming to predict the future of the planet, we first note that since global changes are closely related to this consumption of free energy, and the demands for free energy by human activity are anticipated to increase substantially in the future, the central question in the context of predicting future global change is then how human free energy demands can increase sustainably without negatively impacting the ability of the Earth system to generate free energy. This question could be evaluated with climate models, and the potential deficiencies in these models to adequately represent the thermodynamics of the Earth system are discussed. Then, I illustrate the implications of this thermodynamic perspective by discussing the forms of renewable energy and planetary engineering that would enhance the overall free energy generation and, thereby ‘empower’ the future of the planet

Extracting chemical energy by growing disorder: Efficiency at maximum power

We consider the efficiency of chemical energy extraction from the environment by the growth of a copolymer made of two constituent units in the entropy-driven regime. We show that the thermodynamic nonlinearity associated with the information processing aspect is responsible for a branching of the system properties such as power, speed of growth, entropy production, and efficiency, with varying affinity. The standard linear thermodynamics argument which predicts an efficiency of 1/2 at maximum power is inappropriate because the regime of maximum power is located either outside of the linear regime or on a separate bifurcated branch, and because the usual thermodynamic force is not the natural variable for this optimization.Comment: 6 pages, 4 figure

Diffusion Enhances Chirality Selection

Diffusion effect on chirality selection in a two-dimensional reaction-diffusion model is studied by the Monte Carlo simulation. The model consists of achiral reactants A which turn into either of the chiral products, R or S, in a solvent of chemically inactive vacancies V. The reaction contains the nonlinear autocatalysis as well as recycling process, and the chiral symmetry breaking is monitored by an enantiomeric excess $\phi$. Without dilution a strong nonlinear autocatalysis ensures chiral symmetry breaking. By dilution, the chiral order $\phi$ decreases, and the racemic state is recovered below the critical concentration $c_c$. Diffusion effectively enhances the concentration of chiral species, and $c_c$ decreases as the diffusion coefficient $D$ increases. The relation between $\phi$ and $c$ for a system with a finite $D$ fits rather well to an interpolation formula between the diffusionless(D=0) and homogeneous ($D=\infty$) limits.Comment: 7 pages, 6 figure

Homochiral growth through enantiomeric cross-inhibition

The stability and conservation properties of a recently proposed polymerization model are studied. The achiral (racemic) solution is linearly unstable once the relevant control parameter (here the fidelity of the catalyst) exceeds a critical value. The growth rate is calculated for different fidelity parameters and cross-inhibition rates. A chirality parameter is defined and shown to be conserved by the nonlinear terms of the model. Finally, a truncated version of the model is used to derive a set of two ordinary differential equations and it is argued that these equations are more realistic than those used in earlier models of that form.Comment: 20 pages, 6 figures, Orig. Life Evol. Biosph. (accepted

Reduction of spurious velocity in finite difference lattice Boltzmann models for liquid - vapor systems

The origin of the spurious interface velocity in finite difference lattice Boltzmann models for liquid - vapor systems is related to the first order upwind scheme used to compute the space derivatives in the evolution equations. A correction force term is introduced to eliminate the spurious velocity. The correction term helps to recover sharp interfaces and sets the phase diagram close to the one derived using the Maxwell construction.Comment: 22 pages, 10 figures (submitted to International Journal of Modern Physics C- Physics and Computers

The dynamics of dissipative multi-fluid neutron star cores

We present a Newtonian multi-fluid formalism for superfluid neutron star cores, focussing on the additional dissipative terms that arise when one takes into account the individual dynamical degrees of freedom associated with the coupled "fluids". The problem is of direct astrophysical interest as the nature of the dissipative terms can have significant impact on the damping of the various oscillation modes of the star and the associated gravitational-wave signatures. A particularly interesting application concerns the gravitational-wave driven instability of f- and r-modes. We apply the developed formalism to two specific three-fluid systems: (i) a hyperon core in which both Lambda and Sigma^- hyperons are present, and (ii) a core of deconfined quarks in the colour-flavour-locked phase in which a population of neutral K^0 kaons is present. The formalism is, however, general and can be applied to other problems in neutron-star dynamics (such as the effect of thermal excitations close to the superfluid transition temperature) as well as laboratory multi-fluid systems.Comment: RevTex, no figure

Mirror symmetry breaking as a problem in dynamical critical phenomena

The critical properties of the Frank model of spontaneous chiral synthesis are discussed by applying results from the field theoretic renormalization group (RG). The long time and long wavelength features of this microscopic reaction scheme belong to the same universality class as multi-colored directed percolation processes. Thus, the following RG fixed points (FP) govern the critical dynamics of the Frank model for d<4: one unstable FP that corresponds to complete decoupling between the two enantiomers, a saddle-point that corresponds to symmetric interspecies coupling, and two stable FPs that individually correspond to unidirectional couplings between the two chiral molecules. These latter two FPs are associated with the breakdown of mirror or chiral symmetry. In this simplified model of molecular synthesis, homochirality is a natural consequence of the intrinsic reaction noise in the critical regime, which corresponds to extremely dilute chemical systems.Comment: 9 pages, 3 figure

Nonequilibrium processes in Polymers undergoing Interchange Reactions. Part 2: Reaction-Diffusion Processes

A reactiodffusion system of polymers undergoing interchange reactions is studied. The equation that describes the dynamics of the system is similar to the Boltzmann equation for a gas of hard spheres. We consider a one-dimensionsl system in which the average length and the concentrations at the boundaries are fixed. The resulting steady states are obtained analytically and with numerical integration of equations obtained by using a local equilibrium approximation. Monte Carlo simulations of experimentally realizable conditions were performed and compared. The results reveal a nonlinear distribution of molecular concentration and mass. The entropy of the polymer distributions is calculated as function of position and shown to be less than the entropy for the distributions without interchange reactions. The diffusion of a square pulse is also considered

Total Chiral Symmetry Breaking during Crystallization: Who needs a "Mother Crystal"?

Processes that can produce states of broken chiral symmetry are of particular interest to physics, chemistry and biology. Chiral symmetry breaking during crystallization of sodium chlorate occurs via the production of secondary crystals of the same handedness from a single "mother crystal" that seeds the solution. Here we report that a large and "symmetric" population of D- and L-crystals moves into complete chiral purity disappearing one of the enantiomers. This result shows: (i) a new symmetry breaking process incompatible with the hypothesis of a single "mother crystal"; (ii) that complete symmetry breaking and chiral purity can be achieved from an initial system with both enantiomers. These findings demand a new explanation to the process of total symmetry breaking in crystallization without the intervention of a "mother crystal" and open the debate on this fascinating phenomenon. We present arguments to show that our experimental data can been explained with a new model of "complete chiral purity induced by nonlinear autocatalysis and recycling".Comment: 5 pages, 4 figures, Added reference

Pattern formation from consistent dynamical closures of uniaxial nematic liquid crystals

Pattern formation in uniaxial polymeric liquid crystals is studied for different dynamic closure approximations. Using the principles of mesoscopic non-equilibrium thermodynamics in a mean-field approach, we derive a Fokker-Planck equation for the single-particle non-homogeneous distribution function of particle orientations and the evolution equations for the second and fourth order orientational tensor parameters. Afterwards, two dynamic closure approximations are discussed, one of them considering the relaxation of the fourth order orientational parameter and leading to a novel expression for the free-energy like function in terms of the scalar order parameter. Considering the evolution equation of the density of the system and values of the interaction parameter for which isotropic and nematic phases coexist, our analysis predicts that patterns and traveling waves can be produced in lyotropic uniaxial nematics even in the absence of external driving.Comment: 34 pages, 7 figure