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Thermodynamics

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Thermodynamics

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- Design for Assembly
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- Conversation With Non Muslim - 1 by Moiz Uddin Qidwai
- Thermal Analysis
- Fibre
- 2 Marks Questions 1
- Is Islam Compatible With Democracy?
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- socket
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- Epdm
- IMPORTANT 2 MARKS QUESTIONS
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1 History

as follows, regarding the properties of systems in equilibrium at absolute zero temperature:

during the years 190612, and is therefore often referred

to as Nernsts theorem or Nernsts postulate. The third

The entropy of a perfect crystal, at absolute

law of thermodynamics states that the entropy of a system

zero (zero kelvins), is exactly equal to zero.

at absolute zero is a well-dened constant. This is because

a system at zero temperature exists in its ground state, so

At zero kelvin the system must be in a state with the min- that its entropy is determined only by the degeneracy of

imum possible energy, and this statement of the third law the ground state.

holds true if the perfect crystal has only one minimum energy state. Entropy is related to the number of possible In 1912 Nernst stated the law thus: It is impossible for

microstates, and for a system containing a certain collec- any procedure to lead to the isotherm T = 0 in a nite

[4]

tion of particles, quantum mechanics indicates that there number of steps.

is only one unique state (called the ground state) with An alternative version of the third law of thermodynamics

minimum energy.[1] If the system does not have a well- as stated by Gilbert N. Lewis and Merle Randall in 1923:

dened order (if its order is glassy, for example), then in

practice there will remain some nite entropy as the system is brought to very low temperatures as the system beIf the entropy of each element in some (percomes locked into a conguration with non-minimal enfect) crystalline state be taken as zero at the

ergy. The constant value is called the residual entropy of

absolute zero of temperature, every substance

the system.[2]

has a nite positive entropy; but at the absolute

The NernstSimon statement of the third law of thermozero of temperature the entropy may become

dynamics is in regard to thermodynamic processes, and

zero, and does so become in the case of perwhether it is possible to achieve absolute zero in practice:

fect crystalline substances.

but S itself will also reach zero as long as the crystal has

a ground state with only one conguration. Some crystals form defects which causes a residual entropy. This

residual entropy disappears when the kinetic barriers to

transitioning to one ground state are overcome.[5]

condensed system undergoing a reversible

isothermal process approaches zero as temperature approaches 0 K, where condensed

system refers to liquids and solids.

law of thermodynamics (like the other laws) changed

A simpler formulation of the NernstSimon statement from a fundamental law (justied by experiments) to a

might be:

derived law (derived from even more basic laws). The basic law from which it is primarily derived is the statisticalmechanics denition of entropy for a large system:

It is impossible for any process, no matter how idealized, to reduce the entropy of a

system to its absolute-zero value in a nite

number of operations.

S S0 = kB ln

is the number of microstates consistent with the macroPhysically, the NernstSimon statement implies that it is scopic conguration. The counting of states is from the

impossible for any procedure to bring a system to the ab- reference state of absolute zero, which corresponds to the

solute zero of temperature in a nite number of steps.[3] entropy of S0 .

1

MATHEMATICAL FORMULATION

Explanation

a perfect crystal of a pure substance approaches zero as

the critical temperature approaches zero. The alignment

of a perfect crystal leaves no ambiguity as to the position

of the components of the system and the orientation of

each part of the crystal is identical. As the energy of the

crystal is reduced, the unique vibrations of each atom are

reduced to nothing. At that point no part of the crystal

is unique, hence it is in essence one thing. This law provides an absolute reference point for the determination of

entropy at any other temperature. Any increase in the entropy of a system, determined relative to this zero point,

is the absolute entropy of that system. Mathematically,

the absolute entropy of any system at zero temperature

is the natural log of the number of ground states times

Boltzmanns constant kB=1.38x1023, JK1 .

The entropy of a perfect crystal lattice as dened by

Nernsts theorem is zero provided that its ground state

is unique, because ln(1) = 0. If the system is composed

of one-billion atoms, all alike, and lie within the matrix

of a perfect crystal, the number of permutations of onebillion identical things taken one-billion at a time is =

1. Hence:

S S0 = kB ln = kB ln 1 = 0

The dierence is zero, hence the initial entropy S0 can

be any selected value so long as all other such calculations include that as the initial entropy. As a result the

initial entropy value of zero is selected S0 = 0 is used for

convenience.

S S0 = S 0 = 0

S=0

In way of example, suppose a system consists of 1 cm3

of matter with a mass of 1 g and 20 g/gmole. The system

consists of 3x1022 identical atoms at 0 K. If one atom

should absorb a photon of wavelength of 1 cm that atom

is then unique and the permutations of one unique atom

among the 3x1022 is N=3x1022 . The entropy, energy,

and temperature of the system rises and can be calculated.

The entropy change is:

S = S S0 = kB ln

S = S S0 = kB ln() =

Q

T

S0 = kB ln N = 1.381023 ln 3 1022 = 701023 J/K

The energy change of the system as a result of absorbing

the single photon whose energy is :

Q = =

hc

=

= 21023 J

0.01m

T =

2 1023 J

1

=

=

K

S

70 1023 J/K

35

system over the range from 0 < S < 70x1023 J/K[6] A

single atom was assumed to absorb the photon but the

temperature and entropy change characterizes the entire

system.

An example of a system which does not have a unique

ground state is one whose net spin is a half-integer,

for which time-reversal symmetry gives two degenerate

ground states. For such systems, the entropy at zero

temperature is at least kB*ln(2) (which is negligible on

a macroscopic scale). Some crystalline systems exhibit

geometrical frustration, where the structure of the crystal

lattice prevents the emergence of a unique ground state.

Ground-state helium (unless under pressure) remains liquid.

In addition, glasses and solid solutions retain large entropy at 0 K, because they are large collections of nearly

degenerate states, in which they become trapped out of

equilibrium. Another example of a solid with many

nearly-degenerate ground states, trapped out of equilibrium, is ice Ih, which has proton disorder.

For the entropy at absolute zero to be zero, the magnetic

moments of a perfectly ordered crystal must themselves

be perfectly ordered; from an entropic perspective, this

can be considered to be part of the denition of a perfect crystal. Only ferromagnetic, antiferromagnetic, and

diamagnetic materials can satisfy this condition. Materials that remain paramagnetic at 0 K, by contrast, may

have many nearly-degenerate ground states (for example, in a spin glass), or may retain dynamic disorder (a

quantum spin liquid).

3 Mathematical formulation

S = S S0 =

Hence:

Q

T

system is in equilibrium there are no irreversible processes so the entropy production is zero. During the heat,

4.2

Specic heat

supply temperature gradients are generated in the material, but the associated entropy production can be kept

low enough if the heat is supplied slowly. The increase

in entropy due to the added heat Q is then given by the

second part of the Second law of thermodynamics which

states that the entropy change of a system is given by

The temperature rise dT due to the heat Q is determined

by the heat capacity C(T,X) according to

The parameter X is a symbolic notation for all parameters (such as pressure, magnetic eld, liquid/solid fraction, etc.) which are kept constant during the heat supply.

E.g. if the volume is constant we get the heat capacity

at constant volume CV. In the case of a phase transition

from liquid to solid, or from gas to liquid the parameter X

can be one of the two components. Combining relations

(1) and (2) gives

Integration of Eq.(3) from a reference temperature T 0 to

an arbitrary temperature T gives the entropy at temperature T

We now come to the mathematical formulation of the

third law. There are three steps:

1: in the limit T 0 0 the integral in Eq.(4) is nite. So

that we may take T 0 =0 and write

2. the value of S(0,X) is independent of X. In mathematical form

of steps if S(0,X1 )S(0, X2 ). Right: An innite number of steps

is needed since S(0,X1 )= S(0,X2 ).

third law is explained as follows: Suppose that the temperature of a substance can be reduced in an isentropic

process by changing the parameter X from X2 to X1 . One

can think of a multistage nuclear demagnetization setup

where a magnetic eld is switched on and o in a controlled way.[8] If there were an entropy dierence at absolute zero, T=0 could be reached in a nite number of

steps. However, at T=0 there is no entropy dierence so

an innite number of steps would be needed. The process

is illustrated in Fig.1.

Equation (6) can also be formulated as

isentropic. Eq.(8) is the mathematical formulation of the A non-quantitative description of his third law that Nernst

gave at the very beginning was simply that the specic

third law.

heat can always be made zero by cooling the mate3: as one is free to choose the zero of the entropy it is rial down far enough.[9] A modern, quantitative analyconvenient to take

sis follows. Suppose that the heat capacity of a sample

in the low temperature region can be approximated by

so that Eq.(7) reduces to the nal form

C(T,X)=C 0 T , then

The physical meaning of Eq.(9) is deeper than just a convenient selection of the zero of the entropy. It is due to The integral is nite for T 0 0 if >0. So the heat capacity of all substances must go to zero at absolute zero

the perfect order at zero kelvin as explained before.

4

4.1

Can absolute zero be obtained?

It is impossible by any

procedure, no matter how

idealized, to reduce the

temperature of any system to zero temperature

in a nite number of nite

operations.[7]

monatomic classical ideal gas, such as helium at room

temperature, is given by CV=(3/2)R with R the molar

ideal gas constant. Substitution in Eq.(4) gives

In the limit T 0 0 this expression diverges. Clearly a constant heat capacity does not satisfy Eq.(12). This means

that a gas with a constant heat capacity all the way to absolute zero violates the third law of thermodynamics.

The conict is solved as follows: At a certain temperature

the quantum nature of matter starts to dominate the behavior. Fermi particles follow FermiDirac statistics and

Bose particles follow BoseEinstein statistics. In both

cases the heat capacity at low temperatures is no longer

temperature independent, even for ideal gases. For Fermi

gases

with the Fermi temperature TF given by

7 FURTHER READING

and M the molar mass.

and random processes

Quantum refrigerators

with TB given by

The specic heats given by Eq.(14) and (16) both satisfy

Eq.(12).

4.3

Vapor pressure

Their heat of evaporation has a limiting value given by

with L0 and C constant. If we consider a container, partly

lled with liquid and partly gas, the entropy of the liquid

gas mixture is

where S (T) is the entropy of the liquid and x is the gas

fraction. Clearly the entropy change during the liquidgas

transition (x from 0 to 1) diverges in the limit of T0.

This violates Eq.(8). Nature solves this paradox as follows: at temperatures below about 50 mK the vapor pressure is so low that the gas density is lower than the best

vacuum in the universe. In other words: below 50 mK

there is simply no gas above the liquid.

6 References

[1] J. Wilks The Third Law of Thermodynamics Oxford University Press (1961).

[2] Kittel and Kroemer, Thermal Physics (2nd ed.), page 49.

[3] Wilks, J. (1971). The Third Law of Thermodynamics,

Chapter 6 in Thermodynamics, volume 1, ed. W. Jost,

of H. Eyring, D. Henderson, W. Jost, Physical Chemistry.

An Advanced Treatise, Academic Press, New York, page

477.

[4] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics, New York, ISBN 0883187973, page 342.

[5] Kozliak, Evguenii; Lambert, Frank L. (2008). Residual Entropy, the Third Law and Latent Heat. Entropy 10 (3): 27484. Bibcode:2008Entrp..10..274K.

doi:10.3390/e10030274.

[6] Reynolds and Perkins (1977). Engineering Thermodynamicsq. McGraw Hill. p. 438. ISBN 0-07-052046-1.

4.4

absolute zero at nite pressure. At the melting pressure

liquid and solid are in equilibrium. The third law demands that the entropies of the solid and liquid are equal

at T=0. As a result the latent heat of melting is zero and

the slope of the melting curve extrapolates to zero as a

result of the ClausiusClapeyron equation.

4.5

With the Maxwell relation

and Eq.(8) with X=p it is shown that

So the thermal expansion coecient of all materials must

go to zero at zero kelvin.

See also

Adiabatic process

Ground state

Laws of thermodynamics

Residual entropy

Thermodynamic entropy

[7] Guggenheim, E.A. (1967). Thermodynamics. An Advanced Treatment for Chemists and Physicists, fth revised edition, North-Holland Publishing Company, Amsterdam, page 157.

[8] F. Pobell, Matter and Methods at Low Temperatures,

(Springer-Verlag, Berlin, 2007)

[9] Einstein and the Quantum, A. Douglas Stone, Princeton

University Press, 2013.

7 Further reading

Goldstein, Martin & Inge F. (1993) The Refrigerator

and the Universe. Cambridge MA: Harvard University Press. ISBN 0-674-75324-0. Chpt. 14 is a nontechnical discussion of the Third Law, one including

the requisite elementary quantum mechanics.

Braun, S.; Ronzheimer, J. P.; Schreiber, M.; Hodgman, S. S.; Rom, T.; Bloch, I.; Schneider, U. (2013).

Negative Absolute Temperature for Motional Degrees of Freedom. Science 339 (6115): 52

5. arXiv:1211.0545. Bibcode:2013Sci...339...52B.

doi:10.1126/science.1227831. PMID 23288533.

Lay summary New Scientist (3 January 2013).

Levy, A.; Alicki, R.; Koslo, R. (2012). Quantum refrigerators and the third law of thermodynamics.

Phys.

Rev.

E 85: 061126.

doi:10.1103/PhysRevE.85.061126.

8.1

Text

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