Second law of thermodynamics

Introduction

Versions of the Second 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. Thus, the theorems of thermodynamics can be proved using any form of the second law and third law.

The formulation of the second law that refers to entropy directly is as follows:

In a system, a process that occurs will tend to increase the total entropy of the universe.

Thus, while a system can go through some physical process that decreases its own entropy, the entropy of the universe (which includes the system and its surroundings) must increase overall. (An exception to this rule is a reversible or "isentropic" process, such as frictionless adiabatic compression.) Processes that decrease the total entropy of the universe are impossible. If a system is at equilibrium, by definition no spontaneous processes occur, and therefore the system is at maximum entropy.

A second formulation, due to Rudolf Clausius, is the simplest formulation of the second law, the heat formulation or Clausius statement:

Heat generally cannot flow spontaneously 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 true obviously from ordinary experience. For example in a refrigerator, heat flows from cold to hot, but only when aided by an external agent (i.e. the compressor). Note that from the mathematical definition of entropy, a process in which heat flows from cold to hot has decreasing entropy. This can happen in a non-isolated system 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, by Lord Kelvin, is the heat engine formulation, or Kelvin statement:

It is impossible to convert heat completely into work in a cyclic process.

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. This also means that it is impossible to build solar panels that generate electricity solely from the infrared band of the electromagnetic spectrum without consideration of the temperature on the other side of the panel (as is the case with conventional solar panels that operate in the visible spectrum).

A fourth version of the second law was deduced by the Greek mathematician Constantin Carathéodory. The Carathéodory statement:

In the neighbourhood of any equilibrium state of a thermodynamic system, there are equilibrium states that are adiabatically inaccessible.

A final version of the second law was put to rhyme by Flanders and Swann[1], based on the Clausius statement:

Heat won't pass from a cooler to a hotter
You can try it if you like but you far better notter
'cos the cold in the cooler will get hotter as a ruler
'cos the hotter body's heat will pass to the cooler!

Formulations of the second law in modern textbooks that introduce entropy from the statistical point of view, often contain two parts. The first part states that the entropy of an isolated system cannot decrease, or, to be more precise, the probability of an entropy increase is exceedingly small. The second part gives the relation between infinitesimal entropy increase of a system and an infinitesimal amount of absorbed heat in case of an arbitrary infinitesimal reversible process: $dS = \frac{\delta Q}{T}$. The reason why these two statements are not combined into a single statement is because the first part refers to a general non-equilibrium process in which temperature is not defined.

Descriptions

Informal descriptions

The second law can be stated in various succinct ways, including:

• It is impossible to produce work in the surroundings using a cyclic process connected to a single heat reservoir (Kelvin, 1851).
• It is impossible to carry out a cyclic process using an engine connected to two heat reservoirs that will have as its only effect the transfer of a quantity of heat from the low-temperature reservoir to the high-temperature reservoir (Clausius, 1854).
• If thermodynamic work is to be done at a finite rate, free energy must be expended.[2]

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:[3]

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

where Q is heat, T is temperature and 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 famous version of the second law was read in a presentation at the Philosophical Society of Zurich on April 24, 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 an isolated system undergoing an arbitrary 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 zero. 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.

References

1. http://iankitching.me.uk/humour/hippo/entropy.html
2. Stoner, C.D. (2000). Inquiries into the Nature of Free Energy and Entropy – in Biochemical Thermodynamics. Entropy, Vol 2.
3. Clausius, R. (1865). The Mechanical Theory of Heat – with its Applications to the Steam Engine and to Physical Properties of Bodies. London: John van Voorst, 1 Paternoster Row. MDCCCLXVII.

Faghri, A., and Zhang, Y., 2006, Transport Phenomena in Multiphase Systems, Elsevier, Burlington, MA.

http://en.wikipedia.org/wiki/Second_law_of_thermodynamics - wikipedia.com