Materials Science and Engineering/List of Topics/Thermodynamics/Second Law of Thermodynamics

The second law of thermodynamics is an expression of the universal law of increasing entropy, stating that the entropy of an isolated system which is not in equilibrium will tend to increase over time, approaching a maximum value at equilibrium.

The second law traces its origin to French physicist Sadi Carnot's 1824 paper Reflections on the Motive Power of Fire, which presented the view that motive power (work) is due to the fall of caloric (heat) from a hot to cold body (working substance). In simple terms, the second law is an expression of the fact that over time, ignoring the effects of self-gravity, differences in temperature, pressure, and density tend to even out in a physical system that is isolated from the outside world. Entropy is a measure of how far along this evening-out process has progressed.

There are many versions of the second law, but they all have the same effect, which is to explain the phenomenon of irreversibility in nature.

Statements of the Law
There are many ways of stating the second law of thermodynamics, but all are equivalent in the sense that each form of the second law logically implies every other form (Fermi, 1936). Thus, the theorems of thermodynamics can be proved using any form of the second law.

The formulation of the second law that refers to entropy directly is due to Rudolf Clausius:

In an isolated system, a process can occur only if it increases the total entropy of the system.

Thus, the system can either stay the same, or undergo some physical process that increases entropy. (An exception to this rule is a reversible or "isentropic" process, such as frictionless adiabatic compression.) Processes that decrease total entropy of an isolated system do not occur. If a system is at equilibrium, by definition no spontaneous processes occur, and therefore the system is at maximum entropy.

Also due to Clausius is the simplest formulation of the second law, the heat formulation:

Heat cannot spontaneously flow from a material at lower temperature to a material at higher temperature.

Informally, "Heat doesn't flow from cold to hot (without work input)", which is obviously true from everyday experience. For example in a refrigerator, heat flows from cold to hot, but only when electrical energy is added. Note that from the mathematical definition of entropy, a process in which heat flows from cold to hot has decreasing entropy. This is allowable in a non-isolated system, however only if entropy is created elsewhere, such that the total entropy is constant or increasing, as required by the second law. For example, the electrical energy going into a refrigerator is converted to heat and goes out the back, representing a net increase in entropy.

A third formulation of the second law, the heat engine formulation, by Lord Kelvin, is:

It is impossible to convert heat completely into work.

That is, it is impossible to extract energy by heat from a high-temperature energy source and then convert all of the energy into work. At least some of the energy must be passed on to heat a low-temperature energy sink. Thus, a heat engine with 100% efficiency is thermodynamically impossible.

Mathematical Descriptions
In 1856, the German physicist Rudolf Clausius stated what he called the "second fundamental theorem in the mechanical theory of heat" in the following form:

$$\int \frac{\delta Q}{T} = -N$$

where N is the "equivalence-value" of all uncompensated transformations involved in a cyclical process. Later, in 1865, Clausius would come to define "equivalence-value" as entropy. On the heels of this definition, that same year, the most infamous version of the second law was read in a presentation at the Philosophical Society of Zurich on April 24th, in which, in the end of his presentation, Clausius concludes:

The entropy of the universe tends to a maximum.

This statement is the best-known phrasing of the second law. Moreover, owing to the general broadness of the terminology used here, e.g. universe, as well as lack of specific conditions, e.g. open, closed, or isolated, to which this statement applies, many people take this simple statement to mean that the second law of thermodynamics applies virtually to every subject imaginable. This, of course, is not true; this statement is only a simplified version of a more complex description.

In terms of time variation, the mathematical statement of the second law for a closed system undergoing an adiabatic transformation is:

$$\frac{dS}{dt} \ge 0$$

where


 * S is the entropy and
 * t is time.

It should be noted that statistical mechanics gives an explanation for the second law by postulating that a material is composed of atoms and molecules which are in constant motion. A particular set of positions and velocities for each particle in the system is called a microstate of the system and because of the constant motion, the system is constantly changing its microstate. Statistical mechanics postulates that, in equilibrium, each microstate that the system might be in is equally likely to occur, and when this assumption is made, it leads directly to the conclusion that the second law must hold in a statistical sense. That is, the second law will hold on average, with a statistical variation on the order of 1/√N where N is the number of particles in the system. For everyday (macroscopic) situations, the probability that the second law will be violated is practically nil. However, for systems with a small number of particles, thermodynamic parameters, including the entropy, may show significant statistical deviations from that predicted by the second law. Classical thermodynamic theory does not deal with these statistical variations.

Introduction à la thermodynamique/Deuxième principe de la thermodynamique