This is a really great description on the Fundamental Equations I found online.

© All Rights Reserved

57 tayangan

This is a really great description on the Fundamental Equations I found online.

© All Rights Reserved

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5.1

In Chapter 4, we saw that the entropy is a tool to find the most likely macroscopic state of a

system, i.e., the macroscopic conditions that have the greatest number of microstates. We

also saw that the conditions for equilibrium between two bodies are intimately linked to

derivatives of the entropy. For two single-component systems 1 and 2, there are three

types of equilibrium,

thermal equilibrium:

mechanical (and thermal) equilibrium:

chemical (and thermal) equilibrium:

How do we know that the derivatives of the entropy should involve the quantities , , and

, and not something else? It is precisely because we use equilibrium to measure these

quantities in reality. When we measure temperature, for example, we allow a thermometer

to come to thermal equilibrium with another body with which it exchanges energy. We

then use changes in the properties of the thermometer to characterize the point at which

we have reached thermal equilibrium. We construct a scale called temperature that

depends on these properties. Similarly, we measure pressure by placing a small measuring

device in contact with another body such that the two can exchange volumefor example,

through a piston attached to a spring or through liquid that is displaced in a column. We

can measure the displacement at equilibrium and calculate the net force exerted by both

systems, which must be equal.

Why do the entropy derivatives entail the specific quantities

,

, and

,

where temperature and pressure are on an absolute scale? This will become clearer in our

discussion of work and the first law in the next chapter, but consider for now the following

rough argument. We could construct a temperature- or pressure-measuring device based

on an ideal gas, for which we can determine an explicit, analytical form for the entropy (as

we did roughly in Chapter 2 and will do more thoroughly in Chapter 9). We know that

( )

from this analysis, and experiments on ideal gas volumetric

properties show that this must be equal to the quantity

that we measure in our defined

units. If we bring the ideal gas device to equilibrium with another body, the derivative

relations above must still hold. In this sense the ideal gas can serve as a reference point for

the thermodynamic quantities that determine equilibrium conditions. The fact that the

1

derivatives of the entropy involve inverse temperatures, which may seem confusing at first,

is merely an effect of how scales for measuring hotness developed historically. If we

wanted, we could adopt a coldness scale instead based on

where represents an

infinitely hot state and

is absolute zero.

One way that we know the

and -derivatives of the entropy correspond

to

,

, and

, respectively, is because these are the quantities that

become equal between two bodies at equilibrium, and because any

measurement of

or

necessarily involves bringing a device into

equilibrium with the system of interest. The fact that all of the derivatives

involve inverse temperatures is due to the convention for measuring

hotness.

5.2

fundamental equation,

) is the

(5.1)

We call this particular form of the fundamental equation the entropy version. An equivalent

energy version can be made by rearranging the differentials,

(5.2)

Here, this result describes the function (

as,

(

(5.3)

All that we have done in going from the entropy to energy version is to switch out the

independent variable from to . It is as if we transformed the equation

(

) by

(

)

inverting to solve for as a function of , that is,

(

). Notice also

that the -derivatives depend on the independent variables

.

We must make a brief comment on our notation for the internal energy using the

variable . This convention is to keep consistency with the microscopic picture of matter,

in which the internal energy is the sum of the atomic kinetic energy and potential energy

. An oft-seen alternate convention is the designation of the internal energy as . In order

to avoid confusion with the atomic potential energy, we will forgo this practice, and always

write the total internal energy as .

The reason for transforming to the energy fundamental equation is that it has a

simpler connection to the physical quantities

and . We will work more frequently

with this version because of this simplicity. Note in particular that this equation involves

both extensive and intensive quantities,

An extensive quantity scales linearly with the size of the system. Some

examples are

and . An intensive quantity is independent of the size

of the system upon scaling whilst maintaining the same equilbrium state,

such as

and .

All of the independent variables

and itself are extensive, whereas the derivatives

are intensive. This fact alone means that the function (

) has a very simple form

according to a mathematical argument called Eulers theorem. That form is,

(5.4)

No longer expressed as a differential, this equation gives the integrated form of the

fundamental equation. It shows that the function (

) is given by the sum of the

independent variables times the derivatives of with respect to them. In this expression, it

is important to keep in mind that , , and

are not formally independent, but are

functions of

. It is as if we were to write,

(

(5.5)

) has the special property

that its value for any set of

is also given by the sum on the right hand side of (5.5),

involving derivatives of (

) evaluated at those values.

Eulers theorem applies in this case because of the extensive behavior of the energy.

The proof is as follows. Since scales linearly with system size,

(

(5.6)

(

) (

(

) (

(

)

(

(

)

)

(

(

)

) (

)

(

)

)

(

(

)

)

(

(

(5.7)

Since can be any arbitrary number, Eqn. (5.7) must hold for the case in which

(

)

)

,

(5.8)

That concludes the proof. By an analogous argument, we can construct an integrated form

for the entropy version of the fundamental equation. We can proceed by applying Eulers

(

)

(

), or we can simply

theorem to the extensivity property

rearrange the integrated energy form. Either returns the same result,

(5.9)

EXAMPLE 6.1

Show that the Sackur-Tetrode equation, the exact expression for the entropy of a monatomic ideal gas

with molecular mass , obeys Eulers theorem for the integrated form for the entropy. The SackurTetrode equation is,

[( )

( )]

check Eulers theorem, we must compute the three partial derivatives of ,

)

)

). To

[( )

( )]

(

[( )

( )]

[( )

( )]

5.3

simple: take the ratio of two extensive quantities, such as the energy per particle or the

number of molecules per volume. A common way to construct intensive variables is to use

a per-molecule or per-mole basis, although a per-volume basis would be no less valid. We

will define the energy per particle as follows,

(5.10)

Since the energy is extensive, we can let

4

(5.11)

and volume

Therefore, we can write that is a function of two independent variables,

(

.

(5.12)

variables by one. This occurs because we give up information about the system, and that

information is precisely the system size.

We now seek a fundamental differential equation for (

derivatives. Note that,

(

(5.13)

(

(

(

)

)

)

(

(5.14)

derivative,

(

)

(

)

)

)

(

(5.15)

(5.16)

What happened to the chemical potential when we went to the extensive version? Because

we used the variable to make all quantities intensive, the chemical potential is no longer

a partial of the energy function. Instead, we can recover it using the integrated form of the

fundamental equation,

(5.17)

Rearranging,

(5.18)

This shows that we can still compute the chemical potential from the function ( ).

Therefore, the intensive form of the fundamental equation still contains a relationship to all

intensive variables. This fact has significant implications:

Once and are given, the values of all other intensive variables are fixed at

equilibrium in an isolated, single-component system. is found from ( ),

and stem from derivatives of ( ), and the chemical potential is given

by

. Thus we only need to know two pieces of intensive

information to completely specify the thermodynamic state of the system,

that is, the values of all other intensive variables.

For extensive variables, we need one additional piece of information, the size

of the system .

For systems with more than one component, there will be multiple chemical

potentials (

). Therefore, we would need

more pieces of information to specify the intensive state of a system of

components.

The crux of these statements is very general and powerful: for components, we need

pieces of information to tell us the macroscopic, equilibrium state of a single-phase,

non-reacting system. For multiphase systems, the mere fact that there exists two phases in

equilibrium can serve as one piece of information. For reactive systems, equilibrium

constants serve as additional information. We will learn more about such cases in later

chapters.

Must the two pieces of information specifying the thermodynamic state of a system

be and specifically? It turns out that we can use other sets of parameters by swapping

these variables for their conjugates, the variables that relate to them in the partial

derivatives of the fundamental equation. For example, we can swap for . This is because

we can always regain the value of by solving the following equation at fixed values of

and ,

(

(5.19)

While one might be worried that there are multiple solutions for that satisfy this equality,

the concavity condition on the entropy guarantees that there is only a single one. Similarly,

we can swap for since we could solve,

(

(5.20)

to find as a function of and . Here, the concavity condition also guarantees a single

solution. On the other hand, we cannot swap for because is conjugate to and not .

In that case, there is no concavity condition that could guarantee a unique solution for .

Thus, each piece of information used to specify the thermodynamic state must originate

from different conjugate variable pairs. The same is true if we switch to other intensive

versions of the fundamental equation, e.g., the energy per volume.

The

intensive pieces of information specifying the thermodynamic

state of a system must originate from different conjugate pairs. A conjugate

pair appears as an independent variable and its derivative in a fundamental

) which stem from ( ). In

equation. Examples include ( ) and (

( ) where ( )

general, and are intensive conjugate pairs if

is any intensive fundamental equation.

All thermodynamic variables studied thus far are called state functions, meaning their

values in intensive form are exactly specified once given the

pieces of information

required to specify the equilibrium state. For example, if one prepares a certain singlecomponent system with specific values of and , there is one and only one pressure that

system can exhibit at true equilibrium; no other value will be detected in that system as

long as and remain fixed, unless it strays from equilibrium or, as we will see later, is

metastable. It doesnt matter what processes a system experienced beforehand, or how it

was prepared, the values of state functions will always be the same at the same

thermodynamic state.

The values of state functions are completely determined by the

thermodynamic state of the system, regardless of its history or preparation.

State functions include

and intensive versions thereof.

EXAMPLE 6.2

The energy of a perfect crystal at very low temperatures near absolute zero, and at constant and

conditions, is found to obey

where

and are constants (both proportional to system

size to maintain extensivity). Compute ( ) and ( ).

From the fundamental equation we have,

(

(

Now, we integrate,

(

(

where

is an integration constant. It depends on and

because those were held constant

during the integration. This completes the determination of ( ). To obtain ( ), we backsubstitute for using the measured relation,

(

so that,

(

Alternatively, we could have substituted for

(

)

(

EXAMPLE 6.3

Find the pressure from the above example as (

general, and are - and -dependent.

(

)

[

) ]

Taking the -derivative at constant

(

conditions,

Rearranging, we have,

(

)

]

EXAMPLE 6.4

At constant and , a liquid at its boiling point can also be a vapor or gas. This is similar to the

situation in which there are two systemstwo phasesthat are in equilibrium with each other and

can exchange energy, volume, and particles as the liquid and vapor phases interact. In terms of the

intensive energies and

and volumes

and

(L = liquid, G = gas), write an expression for the

entropy difference

.

Notice here that the two phases reach equilibrium with each other by sharing energy, volume, and

particles. Thus the conditions for thermal, mechanical, and chemical equilibrium apply, meaning

that

,

, and

. If these conditions were not met, phase coexistence would not

be possible; one of the phases would shrink away and the system would become single-phase.

Therefore, we can define the temperatures, pressures, and molar volumes using subscript-less

variables:

,

, and

.

We write out the integrated fundamental equation for

Dividing each side through by the respective

variable,

Notice that the

(

The quantity

appears frequently in thermodynamics, and it is called the molar enthalpy or

per-particle enthalpy,

(

) . We will learn more about the enthalpy in later

chapters, and why it emerges as useful in thermodynamics. For now, we simply show that it relates

conveniently to the entropy associated with a phase transition,

10

Problems

Conceptual and thought problems

1. Starting from the fundamental equation, show that

independent of the size of the system. Use the relation (

that

are independent of .

)

(

) to show

) is enough information to determine the

state of a single-phase, single-component system. Is he or she right or wrong? Explain.

3. For a single-component system, prove that (

( ) where is any extensive quantity.

Fundamentals problems

4. Find the fundamental equation for the intensive quantity

Also give an expression for the pressure in terms of and

.

, in differential form.

. Define

5. An experimentalist measures the molar heat capacity of a system and finds the relation

(

)

( ) . It is also known that the energy and entropy are both zero at absolute

zero. Write an expression for the energy as a function of entropy, ( ). Write an

expression for the equation of state, (

).

Applied problems

6. The term photon gas describes a system in which radiation is inside a rigid container

that is maintained at constant temperature

. In this particular case, the number of

photons is not conserved as they can be created and destroyed. Therefore, it is impossible

to fix the particle number and the chemical potential is always zero. It is also found that

the pressure obeys the relation

entropy and energy are given by the following, where is a volume-dependent constant:

( )

11

12

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