Animated Attractor

Chaos, entropy and the arrow of time

The theory of chaos uncovers a new "uncertainty principle" which governs how the real world behaves. It also explains why time goes in only one direction.

Peter Coveney

Baby and Watches

The nature of time is central not only to our understanding of the world around us, including the physics of how the Universe came into being and how it evolves, but it also affects issues such as the relation between science, culture and human perception. Yet scientists still do not have an easily understandable definition of time.

The problem is that in the everyday world, time appears to go in one direction-it has an arrow. Cups of tea cool, snowmen melt and bulls wreak havoc in china shops. We never see the reverse processes. This unrelenting march of time is captured in thermodynamics, the science of irreversible processes. But underpinning thermodynamics are supposedly more the fundamental laws of the Universe- laws of motion given by Newtonian and quantum mechanics. The equations describing these laws do not distinguish between past and future.Time appears to be a reversible quantity with no arrow.

So we have a conflict between irreversible laws of thermodynamics and the reversible mechanical laws of motion. Does the notion of an arrow of time have to be given up, or do we need to change the fundamental dynamical laws? Today, the theory of chaos can help with the answer.

The second law of thermodynamics is, according to Arthur Eddington, the "supreme law of Nature". It arose from a simple observation: in any macroscopic mechanical process, some or all of the energy always gets dissipated as heat. Just think of rubbing your hands together. In 1850, when Rudolf Clausius, the German physicist, first saw the far-reaching ramifications of this mundane observation, he introduced the concept of "entropy" as a quantity that relentlessly increases because of this heat dissipation. Because heat is the random movement of the individual particles that make up the system, entropy has come to be interpreted as the amount of disorder the system contains. It provides a way of connecting the microscopic world, where Newtonian and quantum mechanics rule, with the macroscopic laws of thermodynamics. For isolated systems that exchange neither energy nor matter with their surroundings, the entropy continues to grow until it reaches its maximum value at what is called thermodynamic equilibrium. This is the final state of the system when there is no change in the macroscopic properties- density, pressure and so on-with time. The concept of equilibrium has proved of great value in thermodynamics. Unfortunately, as a result, most scientists talk about thermodynamics and entropy only in terms of equilibrium states, even though this amounts to a major restriction, as we shall soon see.

It is rare to encounter truly isolated systems. They are more likely to be "closed" (exchanging energy but not matter with the surroundings) or "open" (exchanging both energy and matter). Imagine compressing a gas in a cylinder with a piston. The gas and the cylinder constitute a closed system, so we have to take into account the entropy changes arising from the exchange of energy with the surroundings as well as the entropy change within the gas.

The traditional thermodynamic approach to describing what happens is as follows. The total entropy of the system and the surroundings will be at a maximum for an equilibrium state. This entropy will not change as the volume of the gas is reduced, provided that the gas and the surroundings remain at all instants in equilibrium. This process would be reversible. In order to achieve it, the difference between the external pressure and that of the gas must be infinitesimally small to maintain the state of equilibrium at every moment. In practice, of course, this so-called "quasi-static" compression would take an eternity to perform.

The remarkable conclusion is that equilibrium thermodynamics cannot, therefore, describe change, which is the very means by which we are aware of time. The reason why physicists and chemists rely on equilibrium thermodynamics so much is that it is mathematically easy to use: it produces the quantities, such as entropy, describing the final equilibrium state of an evolving system- Entropy is a so-called thermodynamic "potential".

In reality, all processes take a finite time to happen and, therefore, always proceed out of equilibrium. Theoretically, a system can only aspire to reaching equilibrium, it will never actually reach it. It is, therefore, somewhat ironic that thermodynamicists have focused their attention on the special case of thermodynamic equilibrium. For the difference between equilibrium and non-equilibrium is as stark as that between a journey and its destination, or the words of this sentence and the full stop that ends it. It is only by virtue of irreversible non-equilibrium processes that a system reaches a state of equilibrium. Life itself is a non-equilibrium process: ageing is irreversible. Equilibrium is reached only at death, when a decayed corpse crumbles into dust.

Obviously, you have to use non-equilibrium thermodynamics when dealing with systems that are prevented from reaching equilibrium by external influences, say, where there is a continuous exchange of materials and energy with the environment. Living systems are typical examples.
As an example of a non-equilibrium system, consider an iron rod whose ends are initially at different temperatures. Normally, if one end is hotter than the other, the temperature gradient along the rod would cause the hot end to cool down and the cooler end to warm up until the rod attained a uniform temperature. This is the equilibrium situation. If, however, we maintain one end at a higher temperature, the rod experiences a continual thermodynamic force-a temperature gradient- causing the heat flow, or thermodynamic flux, along the rod. The rod's entropy production is given by the product of the force and the flux, in other words the heat flow multiplied by the temperature gradient.

If the system is close to equilibrium, the fluxes depend in a simple, linear way on the forces: if the force is doubled, then so is the flux. This is linear thermodynamics, which was put on a firm footing by Lars Onsager of Yale University during the 1930s. At equilibrium, the forces vanish and so too do the fluxes.

Ilya Prigogine, a theoretical physicist and physical chemist at the University of Brussels, was the first researcher to tackle entropy in non-equilibrium thermodynamics. In 1945, he showed that for systems close to equilibrium, the thermodynamic potential is the rate at which entropy is produced by the system; this is called "dissipation". Prigogine came up with a theorem of minimum entropy production which predicts that such systems evolve to a steady state that minimises the dissipation. This is reminiscent of equilibrium thermodynamics; the final state is uniform in space and does not vary with time.

Systems far from equilibrium
Prigogine's minimum entropy production theorem is an important result. Together with his colleague Paul Glansdorff and others in Brussels, Prigogine then set out to explore systems maintained even further away from equilibrium, where the linear law for force and flux breaks down, to see whether it was possible to extend his theorem into a general criterion that would work for nonlinear, far- from- equilibrium situations.

Over a period of some 20 years, the research group at Brussels elaborated a theory widely known as "generalised thermodynamics" (a term, in fact, never used by this group). To apply thermodynamic principles to far- from- equilibrium problems, Glansdorff and Prigogine assumed that such systems behave like a good-natured patchwork of equilibrium systems. In this way, entropy and other thermodynamic quantities depend as before, on variables such as temperature and pressure.

Bifurcation Diagram

Systems far from equilibrium can split into two stable states as in figure (a),the slightest tremor triggering many splittings as in (b)

The Glansdorff-Prigogine criterion makes a general statement about the stability of far- from- equilibrium steady states. It says that they may become unstable as they are driven further from equilibrium: there may arise a crisis, or bifurcation point, at which the system prefers to leave the steady state, evolving instead into some other stable state (see Figure la).

The important new possibility is that beyond the first crisis point, highly organised states can suddenly appear. In some non-equilibrium chemical reactions, for example, regular colour changes start to happen so producing "chemical clocks"; in others, beautiful scrolls of colour arise. Such dynamical states are not associated with minimal entropy production by the system; however, the entropy produced is exported to the external environment.

PUSHING THE SECOND LAW TO THE LIMIT. Australian researchers have experimentally shown that microscopic systems (a nano-machine) may spontaneously become more orderly for short periods of time - a development that would be tantamount to violating the second law of thermodynamics, if it happened in a larger system. Don't worry, nature still rigorously enforces the venerable second law in macroscopic systems, but engineers will want to keep limits to the second law in mind when designing nanoscale machines. The new experiment also potentially has important ramifications for an understanding of the mechanics of life on the scale of microbes and cells. There are numerous ways to summarize the second law of thermodynamics. One of the simplest is to note that it's impossible simply to extract the heat energy from some reservoir and use it to do work. Otherwise, machines could run on the energy in a glass of water, for example, by extracting heat and leaving behind a lump of ice. If this were possible, refrigerators and freezers could create electrical power rather that consuming it. The second law typically concerns collections of many trillions of particles - such as the molecules in an iron rod, or a cup of tea, or a helium balloon - and it works well because it is essentially a statistical statement about the collective behavior of countless particles we could never hope to track individually. In systems of only a few particles, the statistics are grainier, and circumstances may arise that would be highly improbable in large systems. Therefore, the second law of thermodynamics is not generally applied to small collections of particles. The experiment at the Australian National University in Canberra and Griffith University in Brisbane (Edith Sevick,, 011+61-2-6125-0508) looks at aspects of thermodynamics in the hazy middle ground between very small and very large systems. The researchers used optical tweezers to grab hold of a micron-sized bead and drag it through water. By measuring the motion of the bead and calculating the minuscule forces on it, the researchers were able to show that the bead was sometimes kicked by the water molecules in such a way that energy was transferred from the water to the bead. In effect, heat energy was extracted from the reservoir and used to do work (helping to move the bead) in apparent violation of the second law. As it turns out, when the bead was briefly moved over short distances, it was almost as likely to extract energy from the water as it was to add energy to the water. But when the bead was moved for more than about 2 seconds at a time, the second law took over again and no useful energy could be extracted from the motion of the water molecules, eliminating the possibility of micron-sized perpetual motion machines that run for more than a few seconds. Nevertheless, many physicists will be surprised to learn that the second law is not entirely valid for systems as large as the bead- and-water experiment, and for periods on the order of seconds. After all, even a cubic micron of water contains about thirty billion molecules. While it's still not possible to do useful work by turning water into ice, the experiment suggests that nanoscale machines may have to deal with phenomena that are more bizarre than most engineers realize. Such tiny devices may even end up running backwards for brief periods due to the counterintuitive energy flow. The research may also be important to biologists because many of the cells and microbes they study comprise systems comparable in size to the bead-and-water experiment.(G.M.Wang et al., Physical Review Letters, 29 July 2002)

As a result, we have to reconsider associating the arrow of time with uniform degeneration into randomness-at least on a local level. At the "end" of time-at equilibrium- randomness may have the last laugh. But over shorter timescales, we can witness the emergence of exquisitely ordered structures which exist as long as the flow of matter and energy is maintained-as illustrated by ourselves, for example.

The Glansdorff-Prigogine criterion is not a universal guiding principle of irreversible evolution because there is an enormous range of possible behaviours available far from equilibrium. How a non-equilibrium system evolves over time can depend very sensitively on the system's microscopic properties-the motions of its constituent atoms and molecules-and not merely on large-scale parameters such as temperature and pressure. Far from equilibrium, the smallest of fluctuations can lead to radically new behaviour on the macroscopic scale. A myriad of bifurcations can carry the system in a random way into new stable states (see Figure lb). These nonuniform states of structural organisation, varying in time or space (or both), were dubbed "dissipative structures" by Prigogine; the spontaneous development of such structures is known as "self-organisation".

Clock and Arrow of Time

Existing thermodynamic theory cannot throw light on the behaviour of non-equilibrium systems beyond the first bifurcation point as we leave equilibrium behind. We can explore such states theoretically only by considering the dynamics of the systems. To describe the one-way evolution of such non- equilibrium systems, we must construct mathematical models based on equations that show how various observable properties of a system change with time.In agreement with the second law of thermodynamics, such sets of equations describing irreversible processes always contain the arrow of time.

Chemical reactions provide typical examples of how this works. We can describe how fast such chemical reactions go as they are driven in the direction of thermodynamic equilibrium in terms of rate laws written in the form of differential equations. The quantities that we can measure are the concentrations of the chemicals involved and the rates at which they change with time.

We do not expect to see self-organising processes in every chemical reaction maintained far from equilibrium. But we often find that the mechanism underlying a reaction leads to differential equations that are nonlinear. Nonlinearities arise, for example, when a certain chemical present enhances (or suppresses) its own production; and they can generate unexpected complexity. Indeed, such nonlinearities are necessary, but not sufficient, for self-organised structures, including deterministic chaos, to appear. An example is the famous Belousov-Zhabotinski reaction discovered in the 1950s, described by Stephen Scott in his recent article on chemical chaos ( "Clocks and chaos in chemistry", New Scientist, 2 December 1989).

Today, as this series of chaos articles admirably shows, many scientists are using nonlinear dynamics to model a dizzying range of complicated phenomena, from fluid dynamics, through chemical and biochemical processes, to genetic variation, heart beats, population dynamics, evolutionary theory and even into economics. The two universal features of all these different phenomena are their irreversibility and their nonlinearity. Deterministic chaos is only one possible consequence; the other is a more regular self-organisation; indeed, chaos is just a special, but very interesting, form of self-organisation in which there is an overload of order.

We can again ask what is the origin of the irreversibility enshrined within the second law of thermodynamics. The traditional reductionist view is that we should seek the explanation on the basis of the reversible mechanical equations of motion. But, as the physicist Ludwig Boltzmann discovered, it is not possible to base the arrow of time directly on equations that ignore it. His failed attempt to reconcile microscopic mechanics with the second law gave rise to the "irreversibility paradox" that I mentioned at the beginning of this article.

The standard way of attempting to derive the equations employed in non-equilibrium thermodynamics starts from the equations of motion, whether classical or quantum mechanical, of the individual particles making up the system, which might, for example, be a gas. Because we cannot know the exact position and velocity of every particle, we have to turn to probability theory-statistical methods-to relate the average behaviour of each particle to the overall behaviour of the system. This is called statistical mechanics. The approach works very well because of the exceedingly large numbers of particles involved (of the order of 1024). The reason for using probabilistic methods is not, merely the practical difficulty of being unable to measure the initial positions and velocities of the participating particles. Quantum mechanics predicts these restrictions as a consequence of Heisenberg's uncertainty principle. But the same is also true for sufficiently unstable chaotic classical dynamical systems. In Ian Percival's article last year ("Chaos: a science for the real world", New Scientist, 21 October 1989), he explained that one of the characteristic features of a chaotic system is its sensitivity to the initial conditions: the behaviour of systems with different initial conditions, no matter how similar, diverges exponentially as time goes on. To predict the future, you would have to measure the initial conditions with literally infinite precision-a task impossible in principle as well as in practice. Again, this means we have to rely on a probabilistic description even at the microscopic level.

Chaotic systems are irreversible in a spectacular way, so we would like to find an entropy-like quantity associated with them because it is entropy that measures change and furnishes the arrow of time. Theorists have made the greatest progress in a class of dynamical systems called ergodic systems. An ergodic system is one which will pass through every possible dynamical state compatible with its energy. The foundations of ergodic theory were laid down by John von Neumann, George Birkhoff, Eberhard Hopf and Paul Halmos during the 1930s and more recently developed by Soviet mathematicians including Andrei Kolmogorov, Dmitrii Anosov, Vladimir Arnold and Yasha Sinai. Their work has revealed that there is a whole hierarchy of behaviours within dynamical systems- some simple, some complex, some paradoxically simple and complex at the same time.

As with the systems described in previous articles on chaos, we can use "phase portraits" to show how an ergodic system behaves. But in this case, we portray the initial state of the system as a bundle of points in phase space, rather than a single point. Figure 2a shows a non-ergodic system: the bundle retains its shape and moves in a periodic fashion over a limited portion of the space. Figure 2b shows an ergodic system; the bundle maintains its shape but now roves around all parts of the space. In Figure 2c the bundle, whose volume must remain constant, spreads out into ever finer fibres, like a drop of ink spreading in water; eventually it invades every part of the space. This is a consequence of what is called Liouville's theorem. In other words, the total probability must be conserved (and add up to 1); the bundle behaves like an incompressible fluid drop. This is an example of a "mixing ergodic flow" , and manifests an approach to thermodynamic equilibrium when the time evolution ceases. Such spreading out implies a form of dynamical chaos. The bundle spreads out because all the trajectories that it contains diverge from each other exponentially fast. Hence it can arise only for a chaotic dynamical system.
Ergodic Systems
The remarkable differences in behavior in "phase space" between a simple system (a),a so-called ergodic system (b) and a mixed ergodic system (c) which is chaotic

Mixing flows are only one member of a hierarchy of increasingly unstable and thus chaotic ergodic dynamical systems. Even more random are the so-called K-flows, named after Kolmogorov. Their behaviour is at the limit of total unpredictability: they have the remarkable property that even an infinite number of prior measurements cannot predict the outcome of the very next measurement. My colleague Baidyanath Misra, working in collaboration with Prigogine, has found an entropy-like quantity with the desired property of increasing with time in this class of highly chaotic systems. The chaotic K-flow property is widespread among systems where collisions between particles dominate the dynamics, from those consisting of just three billiard balls in a box (as shown by Sinai in his pioneering work of 1962) to gases containing many particles considered as hard spheres. Many theorists believe, although they have not yet proved it, that most systems found in everyday life are also K-flows. My colleague, Oliver Penrose of Heriot-Watt University and I are trying to establish, by mathematically rigorous methods, whether we can formulate exact kinetic equations for such systems in the way originally proposed by Boltzmann.

Pocketwatch Globe

In joint research with Maurice Courbage, also at Brussels, Misra and Prigogine discovered a new definition of time for K-flows consistent with irreversibility. This quantity, called the "internal time", represents the age of a dynamical system. You can think of the age as reflecting a system's irreversible thermodynamic aspects, while the description held in Newton's equations for the same system portrays purely reversible dynamical features.

Thermodynamics and mechanics have been pitted against one another for more than a century but now we have revealed a fascinating relationship. Just as with the uncertainty principle in quantum mechanics, where knowing the position of a particle accurately prevents us from knowing its momentum and vice versa, we now find a new kind of uncertainty principle that applies to chaotic dynamical systems. This new principle shows that complete certainty of the thermodynamic properties of a system (through knowledge of its irreversible age) renders the reversible dynamical description meaningless, whilst complete certainty in the dynamical description similarly disables the thermodynamic view.

Understanding dynamical chaos has helped to sharpen our understanding of the concept of entropy. Entropy turns out to be a property of unstable dynamical systems, for which the cherished notion of determinism is overturned and replaced by probabilities and the game of chance. It seems that reversibility and irreversibility are opposite sides of the same coin. As physicists have already found through quantum mechanics, the full structure of the world is richer than our language can express and our brains comprehend. Many deep problems remain open for exploration, but at least we have made a start.

Peter Coveney is a lecturer in physical chemistry at the University of Wales, Bangor. His book, written with Roger Highfield, The Arrow of Time, has just been published by W.H. Allen.

Second Law of Thermodynamics Violated
It seems that something odd happens to the second law of thermodynamics when systems get sufficiently small. The law states that the entropy, or disorder, of the universe increases over time and it holds steadfast for large-scale systems. For instance, whereas a hot beverage will spontaneously dissipate heat to the surrounding air (an increase in disorder), the air cannot heat the liquid without added energy. Nearly a decade ago, scientists predicted that small assemblages of molecules inside larger systems may not always abide by the principle. Now Australian researchers writing in the July 29 issue of Physical Review Letters report that even larger systems of thousands of molecules can also undergo fleeting energy increases that seem to violate the venerable law. Genmiao M. Wang of the Australian National University and colleagues discovered the anomaly when they dragged a micron-sized bead through a container of water using optical tweezers. The team found that, on occasion, the water molecules interacted with the bead in such a way that energy was transferred from the liquid to the bead. These additional kicks used the random thermal motion of the water to do the work of moving the bead, in effect yielding something for nothing. For periods of movement lasting less than two seconds, the bead was almost as likely to gain energy from the water as it was to add energy to the reservoir, the investigators say. No useful amounts of energy could be extracted from the set-up, however, because the effect disappeared if the bead was moved for time intervals greater than two seconds.
The findings suggest that the miniaturization of machines may have inherent limitations. Noting that nanomachines are not simply "rescaled versions of their larger counterparts," the researchers conclude that "as they become smaller, the probability that they will run in reverse inescapably becomes greater." --Sarah Graham
[Scientific American July 30, 2002]

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