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Thermal Dynamic 1

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5.2 Axiomatic Statements of the

Laws of Thermodynamics

5.2.1 Introduction

As a further aid in familiarization with the second law of

thermodynamics and the idea of entropy, we draw an analogy with

statements made previously concerning quantities that are closer to

experience. In particular, we wish to present once more the Zeroth

and First Laws of thermodynamics and use the same framework for

the Second Law. In this so-called ``axiomatic formulation,'' the

parallels between the Zeroth, First and Second Laws will be made

explicit.

5.1

5.2.2 Zeroth Law

Section 1.3.2 presented this observation:

Zeroth Law: There exists for every thermodynamic system in

equilibrium a property called temperature. Equality of temperature is a

necessary and sufficient condition for thermal equilibrium.

The Zeroth law thus defines a property (temperature)

and describes its behavior.

5.2.3 First Law

Observations also show that for any system there is a property called

the energy. The First Law asserts that one must associate such a

property with every system.

First Law: There exists for every thermodynamic system a property

called the energy. The change of energy of a system is equal to the

mechanical work done on the system in an adiabatic process. In a

non-adiabatic process, the change in energy is equal to the heat

added to the system minus the mechanical work done by the system.

On the basis of experimental results, therefore, one is led to assert

the existence of two new properties, the temperature and internal

energy, which do not arise in ordinary mechanics. In a similar way, a

further remarkable relationship between heat and temperature will be

established, and a new property, the entropy, defined. Although this

is a much less familiar property, it is to be stressed that the general

approach is quite like that used to establish the Zeroth and First Laws.

A general principle and a property associated with any system are

extracted from experimental results. Viewed in this way, the entropy

should appear no more mystical than the internal energy. The

increase of entropy in a naturally occurring process is no less real

than the conservation of energy.

5.2.4 Second Law

Although all natural processes must take place in accordance with the

First Law, the principle of conservation of energy is, by itself,

inadequate for an unambiguous description of the behavior of a

system. Specifically, there is no mention of the familiar observation

that every natural process has in some sense a preferred direction of

action. For example, the flow of heat occurs naturally from hotter to

colder bodies, in the absence of other influences, but the reverse flow

certainly is not in violation of the First Law. So far as that law is

concerned, the initial and final states are symmetrical in a very

important respect.

The Second Law is essentially different from the First Law; the two

principles are independent and cannot in any sense be deduced from

one another. Thus, the concept of energy is not sufficient, and a new

property must appear. This property can be developed, and the

Second Law introduced, in much the same way as the Zeroth and

First Laws were presented. By examination of certain observational

results, one attempts to extract from experience a law which is

supposed to be general; it is elevated to the position of a fundamental

axiom to be proved or disproved by subsequent experiments. Within

the structure of classical thermodynamics, there is no proof more

fundamental than observations. A statement which can be adopted as

the Second Law of thermodynamics is:

Second Law: There exists for every thermodynamic system in

equilibrium an extensive scalar property called the entropy, , such

that in an infinitesimal reversible change of state of the

system, , where is the absolute temperature

and is the amount of heat received by the system. The entropy of

a thermally insulated system cannot decrease and is constant if and

only if all processes are reversible.

As with the Zeroth and First Laws, the existence of a new property is

asserted and its behavior is described.

5.2.5 Reversible Processes

In the course of this development, the idea of a completely reversible

process is central, and we can recall the definition, ``a process is

called completely reversible if, after the process has occurred, both

the system and its surroundings can be wholly restored by any means

to their respective initial states'' (first introduced in Section 1.3.3).

Especially, it is to be noted that the definition does not, in this form,

specify that the reverse path must be identical with the forward path. If

the initial states can be restored by any means whatever, the process

is by definition completely reversible. If the paths are identical, then

one usually calls the process (of the system) reversible, or one may

say that the state of the system follows a reversible path. In this path

(between two equilibrium states 1 and 2), (i) the system passes

through the path followed by the equilibrium states only, and (ii) the

system will take the reversed path 2 to 1 by a simple reversal of the

work done and heat added.

Reversible processes are idealizations not actually encountered.

However, they are clearly useful idealizations. For a process to be

completely reversible, it is necessary that it be quasi-static and that

there be no dissipative influences such as friction and diffusion. The

precise (necessary and sufficient) condition to be satisfied if a process

is to be reversible is the second part of the Second Law.

The criterion as to whether a process is completely reversible must be

based on the initial and final states. In the form presented above, the

Second Law furnishes a relation between the properties defining the

two states, and thereby shows whether a natural process connecting

the states is possible.

Muddy Points

What happens when all the energy in the universe is uniformly spread,

i.e., entropy at a maximum? (MP 5.3)

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