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Second law of thermodynamics

From Wikipedia, the free encyclopedia

The second law of thermodynamics is an expression of the tendency that over

time, differences in temperature, pressure, and chemical potential equilibrate in
an isolated physical system. From the state of thermodynamic equilibrium, the
law deduced the principle of the increase of entropy and explains the
phenomenon of irreversibility in nature. The second law declares the impossibility
of machines that generate usable energy from the abundant internal energy of
nature by processes called perpetual motion of the second kind.

The second law may be expressed in many specific ways, but the first formulation
is credited to the French scientist Sadi Carnot in 1824 (see Timeline of
thermodynamics). The law is usually stated in physical terms of impossible
processes. In classical thermodynamics, the second law is a basic postulate
applicable to any system involving measurable heat transfer, while in statistical
thermodynamics, the second law is a consequence of unitarity in quantum theory.
In classical thermodynamics, the second law defines the concept of
thermodynamic entropy, while in statistical mechanics entropy is defined from
information theory, known as the Shannon entropy.

Thermodynamics
Contents
1 Description
1.1 Clausius
statement
1.2 Kelvin Branches
statement Classical · Statistical · Chemical
1.3 Principle of Equilibrium / Non-equilibrium
Carathéodory Thermofluids
1.4 Equivalence
of the Laws
statements Zeroth · First · Second · Third
2 Corollaries
Systems
2.1 Perpetual
motion of the State:
second kind Equation of state
2.2 Carnot Ideal gas · Real gas
theorem Phase of matter · Equilibrium
Control volume · Instruments
2.3 Clausius
theorem
Processes:
2.4

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Thermodynamic Isobaric · Isochoric · Isothermal

temperature Adiabatic · Isentropic · Isenthalpic
Quasistatic · Polytropic
2.5 Entropy
Free expansion
2.6 Available
Reversibility · Irreversibility
useful work
Endoreversibility
3 History
3.1 Informal
Cycles:
descriptions
Heat engines · Heat pumps
3.2 Thermal efficiency
Mathematical
descriptions System properties
4 Derivation from Property diagrams
statistical mechanics Intensive and extensive properties
4.1 Derivation
of the entropy State functions:
change for Temperature / Entropy (intro.) †
reversible Pressure / Volume †
processes Chemical potential / Particle no. †
4.2 Derivation († Conjugate variables)
for systems Vapor quality
described by Reduced properties
the canonical
Process functions:
ensemble
Work · Heat
4.3 General
derivation from Material properties
unitarity of
quantum T
Specific heat capacity c=
mechanics N
5 Non-equilibrium 1
states Compressibility β = −
6 Controversies V
6.1 Maxwell's 1
demon Thermal expansion α =
V
6.2 Loschmidt's
Property database
paradox
6.3 Gibbs Equations
paradox Carnot's theorem
6.4 Poincaré Clausius theorem
recurrence Fundamental relation
theorem Ideal gas law
6.5 Heat death Maxwell relations
of the universe
7 Quotes

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8 Notes Table of thermodynamic equations

9 See also Potentials
10 References Free energy · Free entropy
11 Further reading
12 External links Internal energy U(S,V)
Enthalpy H(S,p) = U + pV
Helmholtz free energy A(T,V) = U − TS
Description Gibbs free energy G(T,p) = H − TS

The first law of thermodynamics History and culture

provides the basic definition of Philosophy:
thermodynamic energy, also Entropy and time · Entropy and life
called internal energy, Brownian ratchet
associated with all Maxwell's demon
thermodynamic systems, but Heat death paradox
unknown in mechanics, and Loschmidt's paradox
states the rule of conservation of Synergetics
energy in nature.
History:
However, the concept of energy General · Heat · Entropy · Gas laws
in the first law does not account Perpetual motion
for the observation that natural Theories:
processes have a preferred Caloric theory · Vis viva
direction of progress. For Theory of heat
example, spontaneously, heat Mechanical equivalent of heat
always flows to regions of lower
Motive power
temperature, never to regions of
Publications:
higher temperature without
"An Experimental Enquiry Concerning ... Heat"
external work being performed
"On the Equilibrium of Heterogeneous Substances"
on the system. The first law is
"Reflections on the
completely symmetrical with
Motive Power of Fire"
respect to the initial and final
states of an evolving system. The
Timelines of:
key concept for the explanation
Thermodynamics · Heat engines
of this phenomenon through the
second law of thermodynamics is Art:
the definition of a new physical
Maxwell's thermodynamic surface
property, the entropy.
Education:
A change in the entropy (S) of a
Entropy as energy dispersal
system is the infinitesimal
transfer of heat (Q) to a closed Scientists
system driving a reversible Daniel Bernoulli
process, divided by the

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equilibrium temperature (T) of Sadi Carnot

the system.[1] Benoît Paul Émile Clapeyron
Rudolf Clausius
Hermann von Helmholtz
Constantin Carathéodory
Pierre Duhem
The entropy of an isolated
Josiah Willard Gibbs
system that is in equilibrium is
James Prescott Joule
constant and has reached its
James Clerk Maxwell
maximum value.
Julius Robert von Mayer
Empirical temperature and its William Rankine
scale is usually defined on the John Smeaton
principles of thermodynamics Georg Ernst Stahl
equilibrium by the zeroth law of Benjamin Thompson
thermodynamics.[2] However, William Thomson, 1st Baron Kelvin
based on the entropy, the second John James Waterston
law permits a definition of the
absolute, thermodynamic
temperature, which has its null point at absolute zero.[3]

The second law of thermodynamics may be expressed in many specific ways, [4]
the most prominent classical statements[3] being the statement by Rudolph
Clausius (1850), the formulation by Lord Kelvin (1851), and the definition in
axiomatic thermodynamics by Constantin Carathéodory (1909). These statements
cast the law in general physical terms citing the impossibility of certain
processes. They have been shown to be equivalent.

Clausius statement

German scientist Rudolf Clausius is credited with the first formulation of the
second law, now known as the Clausius statement:[4]

No process is possible whose sole result is the transfer of heat from a body of
lower temperature to a body of higher temperature.[note 1]

Spontaneously, heat cannot flow from cold regions to hot regions without external
work being performed on the system, which is evident from ordinary experience
of refrigeration, for example. In a refrigerator, heat flows from cold to hot, but
only when forced by an external agent, a compressor.

Kelvin statement

Lord Kelvin expressed the second law in another form. The Kelvin statement
expresses it as follows:[4]

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No process is possible in which the sole result is the absorption of heat from a
reservoir and its complete conversion into work.

This means 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).

Note that it is possible to convert heat completely into work, such as the
isothermal expansion of ideal gas. However, such a process has an additional
result. In the case of the isothermal expansion, the volume of the gas increases
and never goes back without outside interference.

Principle of Carathéodory

Constantin Carathéodory formulated thermodynamics on a purely mathematical

axiomatic foundation. His statement of the second law is known as the Principle of
Carathéodory, which may be formulated as follows:[5]

In every neighborhood of any state S of an adiabatically isolated system there

are states inaccessible from S.[6]

With this formulation he described the concept of adiabatic accessibility for the
first time and provided the foundation for a new subfield of classical
thermodynamics, often called geometrical thermodynamics.

Equivalence of the statements

Suppose there is an engine violating the Kelvin statement: i.e.,one that drains
heat and converts it completely into work in a cyclic fashion without any other
result. Now pair it with a reversed Carnot engine as shown by the graph. The net
and sole effect of this newly created engine consisting of the two engines

mentioned is transferring heat from the cooler reservoir to the

hotter one, which violates the Clausius statement. Thus the Kelvin statement
implies the Clausius statement. We can prove in a similar manner that the
Clausius statement implies the Kelvin statement, and hence the two are
equivalent.

Corollaries

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Perpetual motion of the second

kind

Main article: perpetual motion

Prior to the establishment of the Second

Law, many people who were interested in
inventing a perpetual motion machine
had tried to circumvent the restrictions
of First Law of Thermodynamics by
extracting the massive internal energy of
the environment as the power of the
machine. Such a machine is called a
"perpetual motion machine of the second
kind". The second law declared the
Derive Kelvin Statement from Clausius
impossibility of such machines.
Statement

Carnot theorem

Carnot's theorem (1824) is a principle that limits the maximum efficiency for any
possible engine. The efficiency solely depends on the temperature difference
between the hot and cold thermal reservoirs. Carnot's theorem states:

All irreversible heat engines between two heat reservoirs are less efficient
than a Carnot engine operating between the same reservoirs.
All reversible heat engines between two heat reservoirs are equally
efficient with a Carnot engine operating between the same reservoirs.

In his ideal model, the heat of caloric converted into work could be reinstated by
reversing the motion of the cycle, a concept subsequently known as
thermodynamic reversibility. Carnot however further postulated that some caloric
is lost, not being converted to mechanical work. Hence no real heat engine could
realise the Carnot cycle's reversibility and was condemned to be less efficient.

Though formulated in terms of caloric (see the obsolete caloric theory), rather
than entropy, this was an early insight into the second law.

Clausius theorem

The Clausius theorem (1854) states that in a cyclic process

The equality holds in the reversible case[7] and the '<' is in the irreversible case.

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The reversible case is used to introduce the state function entropy. This is
because in cyclic processes the variation of a state function is zero.

Thermodynamic temperature

Main article: Thermodynamic temperature

For an arbitrary heat engine, the efficiency is:

where A is the work done per cycle. Thus the efficiency depends only on q C/qH.

Carnot's theorem states that all reversible engines operating between the same
heat reservoirs are equally efficient. Thus, any reversible heat engine operating
between temperatures T1 and T2 must have the same efficiency, that is to say, the
effiency is the function of temperatures only:

In addition, a reversible heat engine operating between temperatures T1 and T3

must have the same efficiency as one consisting of two cycles, one between T1
and another (intermediate) temperature T2, and the second between T2 andT3.
This can only be the case if

Now consider the case where T1 is a fixed reference temperature: the

temperature of the triple point of water. Then for any T2 and T3,

Therefore if thermodynamic temperature is defined by

then the function f, viewed as a function of thermodynamic temperature, is simply

and the reference temperature T1 will have the value 273.16. (Of course any
reference temperature and any positive numerical value could be used—the

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choice here corresponds to the Kelvin scale.)

Entropy

Main article: entropy (classical thermodynamics)

According to the Clausius equality, for a reversible process

That means the line integral is path independent.

So we can define a state function S called entropy, which satisfies

With this we can only obtain the difference of entropy by integrating the above
formula. To obtain the absolute value, we need the Third Law of Thermodynamics,
which states that S=0 at absolute zero for perfect crystals.

For any irreversible process, since entropy is a state function, we can always
connect the initial and terminal status with an imaginary reversible process and
integrating on that path to calculate the difference in entropy.

Now reverse the reversible process and combine it with the said irreversible
process. Applying Clausius inequality on this loop,

Thus,

where the equality holds if the transformation is reversible.

Notice that if the process is an adiabatic process, then δQ = 0, so .

Available useful work

See also: Available useful work (thermodynamics)

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An important and revealing idealized special case is to consider applying the

Second Law to the scenario of an isolated system (called the total system or
universe), made up of two parts: a sub-system of interest, and the sub-system's
surroundings. These surroundings are imagined to be so large that they can be
considered as an unlimited heat reservoir at temperature TR and pressure PR —
so that no matter how much heat is transferred to (or from) the sub-system, the
temperature of the surroundings will remain TR; and no matter how much the
volume of the sub-system expands (or contracts), the pressure of the
surroundings will remain PR.

Whatever changes to dS and dSR occur in the entropies of the sub-system and the
surroundings individually, according to the Second Law the entropy Stot of the
isolated total system must not decrease:

According to the First Law of Thermodynamics, the change dU in the internal

energy of the sub-system is the sum of the heat δq added to the sub-system, less
any work δw done by the sub-system, plus any net chemical energy entering the
sub-system d ∑μiRNi, so that:

where μiR are the chemical potentials of chemical species in the external
surroundings.

Now the heat leaving the reservoir and entering the sub-system is

where we have first used the definition of entropy in classical thermodynamics

(alternatively, in statistical thermodynamics, the relation between entropy
change, temperature and absorbed heat can be derived); and then the Second
Law inequality from above.

It therefore follows that any net work δw done by the sub-system must obey

It is useful to separate the work δw done by the subsystem into the useful work
δwu that can be done by the sub-system, over and beyond the work pR dV done
merely by the sub-system expanding against the surrounding external pressure,
giving the following relation for the useful work that can be done:

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It is convenient to define the right-hand-side as the exact derivative of a

thermodynamic potential, called the availability or exergy X of the subsystem,

The Second Law therefore implies that for any process which can be considered
as divided simply into a subsystem, and an unlimited temperature and pressure
reservoir with which it is in contact,

i.e. the change in the subsystem's exergy plus the useful work done by the
subsystem (or, the change in the subsystem's exergy less any work, additional to
that done by the pressure reservoir, done on the system) must be less than or
equal to zero.

In sum, if a proper infinite-reservoir-like reference state is chosen as the system

surroundings in the real world, then the Second Law predicts a decrease in X for
an irreversible process and no change for a reversible process.

Is equivalent to

This expression together with the associated reference state permits a design
engineer working at the macroscopic scale (above the thermodynamic limit) to
utilize the Second Law without directly measuring or considering entropy change
in a total isolated system. (Also, see process engineer). Those changes have
already been considered by the assumption that the system under consideration
can reach equilibrium with the reference state without altering the reference
state. An efficiency for a process or collection of processes that compares it to the
reversible ideal may also be found (See second law efficiency.)

This approach to the Second Law is widely utilized in engineering practice,

environmental accounting, systems ecology, and other disciplines.to the formal
energy created may not be supportive but it can be created from one form to
another form ..it can be also called as conservation of energy .,

History
See also: History of entropy

The first theory of the conversion of heat into mechanical work is due to Nicolas
Léonard Sadi Carnot in 1824. He was the first to realize correctly that the
efficiency of this conversion depends on the difference of temperature between an
engine and its environment.

Recognizing the significance of James Prescott Joule's work on the conservation of

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energy, Rudolf Clausius was the first to formulate the second law during 1850, in
this form: heat does not flow spontaneously from cold to hot bodies. While
common knowledge now, this was contrary to the caloric theory of heat popular at
the time, which considered heat as a fluid. From there he was able to infer the
principle of Sadi Carnot and the definition of entropy (1865).

Established during the 19th century, the Kelvin-Planck statement of the Second
Law says, "It is impossible for any device that operates on a cycle to receive heat
from a single reservoir and produce a net amount of work." This was shown to be
equivalent to the statement of Clausius.

The ergodic hypothesis is also important for the Boltzmann approach. It says that,
over long periods of time, the time spent in some region of the phase space of
microstates with the same energy is proportional to the volume of this region, i.e.
that all accessible microstates are equally probable over a long period of time.
Equivalently, it says that time average and average over the statistical ensemble
are the same.

It has been shown that not only classical systems but also quantum mechanical
ones tend to maximize their entropy over time. Thus the second law follows, given
initial conditions with low entropy. More precisely, it has been shown that the
local von Neumann entropy is at its maximum value with a very high
probability.[8] The result is valid for a large class of isolated quantum systems
(e.g. a gas in a container). While the full system is pure and therefore does not
have any entropy, the entanglement between gas and container gives rise to an
increase of the local entropy of the gas. This result is one of the most important
achievements of quantum thermodynamics.

Today, much effort in the field is attempting to understand why the initial
conditions early in the universe were those of low entropy, [9][10] as this is seen as
the origin of the second law (see below).

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.[11]

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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: [12]

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:

where

S is the entropy and

t is time.

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

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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.

Derivation from statistical mechanics

In statistical mechanics,the Second Law is not a postulate, rather it is a
consequence of the fundamental postulate, also known as the equal prior
probability postulate, so long as one is clear that simple probability arguments
are applied only to the future, while for the past there are auxiliary sources of
information which tell us that it was low entropy. The first part of the second law,
which states that the entropy of a thermally isolated system can only increase is a
trivial consequence of the equal prior probability postulate, if we restrict the
notion of the entropy to systems in thermal equilibrium. The entropy of an
isolated system in thermal equilibrium containing an amount of energy of E is:

where is the number of quantum states in a small interval between E and

E + δE. Here δE is a macroscopically small energy interval that is kept fixed.
Strictly speaking this means that the entropy depends on the choice of δE.
However, in the thermodynamic limit (i.e. in the limit of infinitely large system
size), the specific entropy (entropy per unit volume or per unit mass) does not
depend on δE.

Suppose we have an isolated system whose macroscopic state is specified by a

number of variables. These macroscopic variables can, e.g., refer to the total
volume, the positions of pistons in the system, etc. Then Ω will depend on the
values of these variables. If a variable is not fixed, (e.g. we do not clamp a piston
in a certain position), then because all the accessible states are equally likely in
equilibrium, the free variable in equilibrium will be such that Ω is maximized as
that is the most probable situation in equilibrium.

If the variable was initially fixed to some value then upon release and when the
new equilibrium has been reached, the fact the variable will adjust itself so that Ω
is maximized, implies that the entropy will have increased or it will have stayed
the same (if the value at which the variable was fixed happened to be the
equilibrium value).

The entropy of a system that is not in equilibrium can be defined as:

see here. Here the Pj is the probabilities for the system to be found in the states

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labeled by the subscript j. In thermal equilibrium the probabilities for states

inside the energy interval δE are all equal to 1 / Ω, and in that case the general
definition coincides with the previous definition of S that applies to the case of
thermal equilibrium.

Suppose we start from an equilibrium situation and we suddenly remove a

constraint on a variable. Then right after we do this, there are a number Ω of
accessible microstates, but equilibrium has not yet been reached, so the actual
probabilities of the system being in some accessible state are not yet equal to the
prior probability of 1 / Ω. We have already seen that in the final equilibrium state,
the entropy will have increased or have stayed the same relative to the previous
equilibrium state. Boltzmann's H-theorem, however, proves that the entropy will
increase continuously as a function of time during the intermediate out of
equilibrium state.

Derivation of the entropy change for reversible processes

The second part of the Second Law states that the entropy change of a system
undergoing a reversible process is given by:

where the temperature is defined as:

See here for the justification for this definition. Suppose that the system has some
external parameter, x, that can be changed. In general, the energy eigenstates of
the system will depend on x. According to the adiabatic theorem of quantum
mechanics, in the limit of an infinitely slow change of the system's Hamiltonian,
the system will stay in the same energy eigenstate and thus change its energy
according to the change in energy of the energy eigenstate it is in.

The generalized force, X, corresponding to the external variable x is defined such

that Xdx is the work performed by the system if x is increased by an amount dx.
E.g., if x is the volume, then X is the pressure. The generalized force for a system
known to be in energy eigenstate Er is given by:

Since the system can be in any energy eigenstate within an interval of δE, we
define the generalized force for the system as the expectation value of the above
expression:

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To evaluate the average, we partition the energy eigenstates by counting

how many of them have a value for within a range between Y and Y + δY.
Calling this number , we have:

The average defining the generalized force can now be written:

We can relate this to the derivative of the entropy w.r.t. x at constant energy E as
follows. Suppose we change x to x + dx. Then will change because the
energy eigenstates depend on x, causing energy eigenstates to move into or out of
the range between E and E + δE. Let's focus again on the energy eigenstates for
which lies within the range between Y and Y + δY. Since these energy
eigenstates increase in energy by Y dx, all such energy eigenstates that are in the
interval ranging from E - Y dx to E move from below E to above E. There are

such energy eigenstates. If , all these energy eigenstates will move into
the range between E and E + δE and contribute to an increase in Ω. The
number of energy eigenstates that move from below E + δE to above E + δE is,
of course, given by . The difference

is thus the net contribution to the increase in Ω. Note that if Y dx is larger than
δE there will be the energy eigenstates that move from below E to above
E + δE. They are counted in both and , therefore the above
expression is also valid in that case.

Expressing the above expression as a derivative w.r.t. E and summing over Y

yields the expression:

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The logarithmic derivative of Ω w.r.t. x is thus given by:

The first term is intensive, i.e. it does not scale with system size. In contrast, the
last term scales as the inverse system size and will thus vanishes in the
thermodynamic limit. We have thus found that:

Combining this with

Gives:

Derivation for systems described by the canonical ensemble

If a system is in thermal contact with a heat bath at some temperature T then, in

equilibrium, the probability distribution over the energy eigenvalues are given by
the canonical ensemble:

Here Z is a factor that normalizes the sum of all the probabilities to 1, this
function is known as the partition function. We now consider an infinitesimal
reversible change in the temperature and in the external parameters on which the
energy levels depend. It follows from the general formula for the entropy:

that

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Inserting the formula for Pj for the canonical ensemble in here gives:

General derivation from unitarity of quantum mechanics

The time development operator in quantum theory is unitary, because the

Hamiltonian is hermitian. Consequently the transition probability matrix is doubly
stochastic, which implies the Second Law of Thermodynamics.[13][14] This
derivation is quite general, based on the Shannon entropy, and does not require
any assumptions beyond unitarity, which is universally accepted. It is a
consequence of the irreversibility or singular nature of the general transition
matrix.

Non-equilibrium states
Statistically it is possible for a system to achieve moments of non-equilibrium. In
such statistically unlikely events where hot particles "steal" the energy of cold
particles enough that the cold side gets colder and the hot side gets hotter, for an
instant. Such events have been observed at a small enough scale where the
likelihood of such a thing happening is significant.[15] The physics involved in
such an event is described by the fluctuation theorem.

Controversies
Maxwell's demon

Main article: Maxwell's demon

James Clerk Maxwell imagined one container divided into two parts, A and B.
Both parts are filled with the same gas at equal temperatures and placed next to
each other. Observing the molecules on both sides, an imaginary demon guards a
trapdoor between the two parts. When a faster-than-average molecule from A flies
towards the trapdoor, the demon opens it, and the molecule will fly from A to B.
The average speed of the molecules in B will have increased while in A they will
have slowed down on average. Since average molecular speed corresponds to
temperature, the temperature decreases in A and increases in B, contrary to the
second law of thermodynamics.

One of the most famous responses to this question was suggested in 1929 by Leó

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Szilárd and later by Léon Brillouin. Szilárd pointed out that a real-life Maxwell's
demon would need to have some means of measuring molecular speed, and that
the act of acquiring information would require an expenditure of energy. But later
exceptions were found.

Loschmidt's paradox

Loschmidt's paradox, also known as the reversibility paradox, is the objection that
it should not be possible to deduce an irreversible process from time-symmetric
dynamics. This puts the time reversal symmetry of (almost) all known low-level
fundamental physical processes at odds with any attempt to infer from them the
second law of thermodynamics which describes the behavior of macroscopic
systems. Both of these are well-accepted principles in physics, with sound
observational and theoretical support, yet they seem to be in conflict; hence the
paradox.

One approach to handling Loschmidt's paradox is the fluctuation theorem, proved

by Denis Evans and Debra Searles, which gives a numerical estimate of the
probability that a system away from equilibrium will have a certain change in
entropy over a certain amount of time. The theorem is proved with the exact time
reversible dynamical equations of motion and the Axiom of Causality. The
fluctuation theorem is proved utilizing the fact that dynamics is time reversible.
Quantitative predictions of this theorem have been confirmed in laboratory
experiments at the Australian National University conducted by Edith M. Sevick
et al. using optical tweezers apparatus.

Gibbs paradox

Main article: Gibbs paradox

In statistical mechanics, a simple derivation of the entropy of an ideal gas based

on the Boltzmann distribution yields an expression for the entropy which is not
extensive (is not proportional to the amount of gas in question). This leads to an
apparent paradox known as the Gibbs paradox, allowing, for instance, the entropy
of closed systems to decrease, violating the second law of thermodynamics.

The paradox is averted by recognizing that the identity of the particles does not
influence the entropy. In the conventional explanation, this is associated with an
indistinguishability of the particles associated with quantum mechanics. However,
a growing number of papers now take the perspective that it is merely the
definition of entropy that is changed to ignore particle permutation (and thereby
avert the paradox). The resulting equation for the entropy (of a classical ideal gas)
is extensive, and is known as the Sackur-Tetrode equation.

Poincaré recurrence theorem

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The Poincaré recurrence theorem states that certain systems will, after a
sufficiently long time, return to a state very close to the initial state. The Poincaré
recurrence time is the length of time elapsed until the recurrence, which is of the
order of .[16] The result applies to physical systems in which energy is
conserved. The Recurrence theorem apparently contradicts the Second law of
thermodynamics, which says that large dynamical systems evolve irreversibly
towards the state with higher entropy, so that if one starts with a low-entropy
state, the system will never return to it. There are many possible ways to resolve
this paradox, but none of them is universally accepted[citation needed]. The most
typical argument is that for thermodynamical systems like an ideal gas in a box,
recurrence time is so large that for all practical purposes it is infinite.

Heat death of the universe

Main article: Heat death of the universe

According to the second law, the entropy of any isolated system, such as the
entire universe, never decreases. If the entropy of the universe has a maximum
upper bound then when this bound is reached the universe has no thermodynamic
free energy to sustain motion or life, that is, the heat death is reached.

Quotes
The law that entropy always increases holds, I think, the supreme
position among the laws of Nature. If someone points out to you that
your pet theory of the universe is in disagreement with Maxwell's
equations — then so much the worse for Maxwell's equations. If it is
found to be contradicted by observation — well, these experimentalists
do bungle things sometimes. But if your theory is found to be against
the second law of thermodynamics I can give you no hope; there is
nothing for it but to collapse in deepest humiliation.
—Sir Arthur Stanley Eddington, The Nature of the Physical World
(1927)

The tendency for entropy to increase in isolated systems is expressed in

the second law of thermodynamics — perhaps the most pessimistic and
amoral formulation in all human thought.
—Gregory Hill and Kerry Thornley, Principia Discordia (1965)

There are almost as many formulations of the second law as there have
been discussions of it.
—Philosopher / Physicist P.W. Bridgman, (1941)

Notes

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1. ^ Translated from German original: Es gibt keine Zustandsänderung, deren einziges

Ergebnis die Übertragung von Wärme von einem Körper niederer auf einen Körper
höherer Temperatur ist.

See also
Jarzynski equality
Clausius–Duhem inequality Laws of thermodynamics
Constructal law Maximum entropy
Entropy thermodynamics
Entropy (arrow of time) Reflections on the Motive
Entropy: A New World View Power of Fire [book]
[book] Statistical mechanics
First law of thermodynamics Thermal diode
History of thermodynamics Relativistic heat conduction
Second-law efficiency

References
1. ^ A. Bejan, (2006). 'Advanced Engineering Thermodynamics', Wiley. ISBN
0-471-67763-9
2. ^ J. S. Dugdale (1996, 1998). Entropy and its Physical Meaning. Tayler & Francis.
p. 13. ISBN 9-7484-0569-0. "This law is the basis of temperature."
3. ^ a b E. H. Lieb, J. Yngvason (1999). "The Physics and Mathematics of the Second
Law of Thermodynamics". Physics Reports 310: 1–96. arXiv:cond-mat/9708200
(http://arxiv.org/abs/cond-mat/9708200) . Bibcode 1999PhR...310....1L
(http://adsabs.harvard.edu/abs/1999PhR...310....1L) .
doi:10.1016/S0370-1573(98)00082-9 (http://dx.doi.org
/10.1016%2FS0370-1573%2898%2900082-9) .
4. ^ a b c "Concept and Statements of the Second Law" (http://web.mit.edu/16.unified
/www/FALL/thermodynamics/notes/node37.html) . web.mit.edu. http://web.mit.edu
/16.unified/www/FALL/thermodynamics/notes/node37.html. Retrieved 2010-10-07.
5. ^ C. Caratheodory (1909). "Untersuchungen über die Grundlagen der
Thermodynamik". Mathematische Annalen 67: 363. "Axiom II: In jeder beliebigen
Umgebung eines willkürlich vorgeschriebenen Anfangszustandes gibt es Zustände,
die durch adiabatische Zustandsänderungen nicht beliebig approximiert werden
können."
6. ^ H.A. Buchdahl (1966). The Concepts of Classical Thermodynamics. Cambridge
University Press. p. 68.
7. ^ Clausius theorem (http://scienceworld.wolfram.com/physics
/ClausiusTheorem.html) at Wolfram Research
8. ^ Gemmer, Jochen; Otte, Alexander; Mahler, Günter (2001). "Quantum Approach to a
Derivation of the Second Law of Thermodynamics". Physical Review Letters 86 (10):
1927–1930. arXiv:quant-ph/0101140 (http://arxiv.org/abs/quant-ph/0101140) .
Bibcode 2001PhRvL..86.1927G (http://adsabs.harvard.edu/abs/2001PhRvL..86.1927G)

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. doi:10.1103/PhysRevLett.86.1927 (http://dx.doi.org
/10.1103%2FPhysRevLett.86.1927) . PMID 11289822 (http://www.ncbi.nlm.nih.gov
/pubmed/11289822)
9. ^ Carroll; Jennifer Chen (2335). "Does Inflation Provide Natural Initial Conditions for
the Universe?". Gen.Rel.Grav. () ; International Journal of Modern Physics D D14 ()
-2340 37 (2005): 1671–1674. arXiv:gr-qc/0505037 (http://arxiv.org/abs/gr-
qc/0505037) . Bibcode 2005GReGr..37.1671C (http://adsabs.harvard.edu
/abs/2005GReGr..37.1671C) . doi:10.1007/s10714-005-0148-2 (http://dx.doi.org
/10.1007%2Fs10714-005-0148-2) .
10. ^ Wald, R (2006). "The arrow of time and the initial conditions of the universe".
Studies in History and Philosophy of Science Part B: Studies in History and
Philosophy of Modern Physics 37 (3): 394–398. doi:10.1016/j.shpsb.2006.03.005
(http://dx.doi.org/10.1016%2Fj.shpsb.2006.03.005) .
11. ^ Stoner (2000). "Inquiries into the Nature of Free Energy and Entropy in Respect to
Biochemical Thermodynamics". Entropy 2 (3): 106–141. arXiv:physics/0004055
(http://arxiv.org/abs/physics/0004055) . Bibcode 2000Entrp...2..106S
(http://adsabs.harvard.edu/abs/2000Entrp...2..106S) . doi:10.3390/e2030106
(http://dx.doi.org/10.3390%2Fe2030106) .
12. ^ 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.
13. ^ Hugh Everett, "Theory of the Universal Wavefunction" (http://www.pbs.org
/wgbh/nova/manyworlds/pdf/dissertation.pdf) , Thesis, Princeton University, (1956,
1973), Appendix I, pp 121 ff, in particular equation (4.4) at the top of page 127, and
the statement on page 29 that "it is known that the [Shannon] entropy [...] is a
monotone increasing function of the time."
14. ^ Bryce Seligman DeWitt, R. Neill Graham, eds, The Many-Worlds Interpretation of
Quantum Mechanics, Princeton Series in Physics, Princeton University Press (1973),
ISBN 0-691-08131-X Contains Everett's thesis: The Theory of the Universal
Wavefunction, pp 3-140.
15. ^ Wang, G.; Sevick, E.; Mittag, Emil; Searles, Debra; Evans, Denis (2002).
"Experimental Demonstration of Violations of the Second Law of Thermodynamics for
Small Systems and Short Time Scales". Physical Review Letters 89 (5). Bibcode
2002PhRvL..89e0601W (http://adsabs.harvard.edu/abs/2002PhRvL..89e0601W) .
doi:10.1103/PhysRevLett.89.050601 (http://dx.doi.org
/10.1103%2FPhysRevLett.89.050601) .
16. ^ L. Dyson, J. Lindesay and L. Susskind, Is There Really a de Sitter/CFT Duality, JHEP
0208, 45 (2002)

Further reading
Goldstein, Martin, and Inge F., 1993. The Refrigerator and the Universe.
Harvard Univ. Press. Chpts. 4-9 contain an introduction to the Second
Law, one a bit less technical than this entry. ISBN 978-0-674-75324-2
Leff, Harvey S., and Rex, Andrew F. (eds.) 2003. Maxwell's Demon 2 :
Entropy, classical and quantum information, computing. Bristol UK;

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Philadelphia PA: Institute of Physics. ISBN 978-0-585-49237-7

Halliwell, J.J. et al. (1994). Physical Origins of Time Asymmetry.
Cambridge. ISBN 0-521-56837-4.(technical).
Iftime (2010). "Complex aspects of gravity". arXiv:1001.4571
(http://arxiv.org/abs/1001.4571) [physics.gen-ph (http://arxiv.org/archive
/physics.gen-ph) ].
Carnot, Sadi; Thurston, Robert Henry (editor and translator) (1890).
Reflections on the Motive Power of Heat and on Machines Fitted to
Develop That Power. New York: J. Wiley & Sons. (full text of 1897 ed.)
(http://books.google.com/books?id=tgdJAAAAIAAJ) ) (html
(http://www.history.rochester.edu/steam/carnot/1943/) )

External links
Stanford Encyclopedia of Philosophy: "Philosophy of Statistical Mechanics
(http://plato.stanford.edu/entries/statphys-statmech/) " -- by Lawrence
Sklar.
Second law of thermodynamics (http://web.mit.edu/16.unified/www/FALL
/thermodynamics/notes/node30.html) in the MIT Course Unified
Thermodinamics and Propulsion (http://web.mit.edu/16.unified/www/FALL
/thermodynamics/notes/notes.html) from Prof. Z. S. Spakovszky
E.T. Jaynes, 1988, "The evolution of Carnot's principle,
(http://bayes.wustl.edu/etj/articles/ccarnot.pdf) " in G. J. Erickson and C.
R. Smith (eds.)Maximum-Entropy and Bayesian Methods in Science and
Engineering, Vol 1, p. 267.
Website devoted to the Second Law. (http://www.secondlaw.com/)

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