Thermodynamic Property Relation

1. Introduction. Application of thermodynamic principles to engineering systems requires data such as internal energy, enthalpy, entropy, and other properties. The objective of the present chapter is to introduce mathematical interrelations of thermodynamic properties of simple compressible systems to be evaluated from data that are more readily measured such as p, v, T. All other intensive properties, such as h, u, etc., can be determined as a function of two independent properties (e.g. p and T).

2. Mathematical Relations. Certain mathematical manipulations are repeatedly useful and these are now briefly reviewed. If z = f (x, y), where x, y, z here represent any three properties of a pure substance, then it is always true that ( ) ( )

which in words says that a change in the property z can be considered as occurring in two steps, one step while y is constant, say, and another while x is constant, say, y y ⁄ . Equation (2.1a) is the exact differential of z, and can also be written as x x

where: M = coefficient of dx N = coefficient of dy This two-step change in property can be illustrated using the T-s diagram in Figure 2.1 below:

To find the change of entropy from point 1 to 2 we consider the change to occur in two steps: first, change in entropy with respect to T while p is constant; second, change in entropy with respect to p while T is constant. From this, entropy can be expressed as s = f (p, T), then the change in entropy ( where: s = entropy T = temperature P = pressure the differential ds must always be an exact differential (that is, a point function rather than a path function), and an equation relating a point function must meet the test for exactness to be valid. This test is that the derivatives of the coefficient of dx and dy in Eq. 2.1a are equal ( or ( ) ( ) ) *( ) + ( ) *( ) + ) ( )

the exactness test will be used later to obtain the Maxwell relations.

3. Maxwell Relations The Maxwell relations apply to pure substances in processes involving heat, work, and internal energy, and they are useful in mathematical manipulations, especially as it is desired to eliminate entropy in favor of p, v, T, or to determine an entropy change from p, v, T data. Maxwell relations are found by applying the exactness test, shown by (2.3b), to the functions of the properties internal energy, enthalpy, Helmholtz function, and Gibbs function. These properties are given below. Internal energy:

Enthalpy:

Helmholtz function:

Gibbs function:

where: u = internal energy h = enthalpy A = Helmholtz function G = Gibbs function

T = temperature p = pressure v = specific volume

the derivations for equations (3.1) through (3.4) are shown below. Derivation for Internal Energy: In the absence of kinetic energy and potential energy the heat equation can be written as

where: q = heat w = work but:

substituting (3.5b) and (3.5c) to (3.5a) yields

or

Derivation for Enthalpy: We start with the basic equation for enthalpy

thus

substituting (3.1) to (3.6b) yields

Derivation for Helmholtz function: Helmholtz function, A is defined as

thus

Substituting (3.1) to (3.7b) yields

Derivation for Gibbs function: Gibbs function, G is defined as

thus

substituting (3.2) to (3.8b) yields

The Helmholtz and Gibbs functions are properties because each is defined in terms of properties. From inspection of Equations (3.3) and (3.4), the units of A and G are the same as those of u and h. these two properties are introduced solely because they contribute to the present discussion, and no physical significance need be attached to them at this point. The four differential equations introduced above, Equations (3.1), (3.2), (3.3), and (3.4), provide the basis for several important property relations. Since only properties are involved, each is an exact differential exhibiting the general form . Underlying these exact differentials are, respectively, functions of the form , , , . Let us consider these functions in the order given. The differential of the function is ( or ) ( )

by inspection ( ( ) )

by applying the exactness test from (2.3b), the Maxwell relation is ( ) ( )

The differential of the function ( or )

is ( )

by inspection ( ( the Maxwell relation is ( The differential for the function ( or ) ) ( ) is ( ) ) )

by inspection ( ( the Maxwell relation is ( The differential for the function ( or ) ) ( ) is ( ) ) )

by inspection ( ( the Maxwell relation is ( ) ( ) ) )

Table 3.1 shows a summary of the Maxwell relations previously derived.

Table 3.1: Summary of Maxwell Relations Functions Maxwell Relations I. ( II. ( III. ( ) ( ) ) ( ) ) ( )

IV. ( ) ( )

It will be convenient to refer to the various Maxwell relations be their Roman numerals in Table 3.1; relation I is .

Other common relations involving p, v, T, and s: ( ) ( ) ( ) ( )

(

)

(

)

(

)

(

)

4. Clausius-Clapeyron Equation With the introduction to the Maxwell relations, we are in a position to develop thermodynamic relations that will allow changes in entropy, internal energy, and enthalpy to be evaluated from measured property data. As an immediate application of Maxwell’s relations, we shall derive the Clausius-Clapeyron equation, also often called the Clapeyron equation. The Clapeyron equation allows the change in enthalpy during vaporization, sublimation, or melting at constant temperature to be evaluated from pressure-specific volume-temparature data pertaining to the phase change. One way of deriving the Clapeyron equation is to use the Maxwell relation III. ( ) ( )

Let us consider a process of vaporization under equilibrium conditions. For such a process, T = C, and the pressure and temperature are not a function of volume. Integrating the right-hand side from saturated liquid to saturated vapor at a particular p, T

( (

)∫ )( ( ) )

We know from Equation (3.2) that , but for vaporization . Thus, or . Substituting this to (4.1) yields the Clapeyron equation ( )

where is the slope of the curve separating the liquid and vapor phases on the pT plane, Fig. 4.1. This important equation is useful (1) for checking the consistency of experimental data, (2) especially for determining the latent heat of vaporization from only p, v, T data, (3)

finding any one of the terms in the equation when all others are known, (4) for a possible ⁄ definition of absolute temperature, ( ⁄ ) .

The same idea can be applied to the two-phase solid-liquid systems, in which the slope of the curve separating the solid and liquid phases, Fig. 4.1. For this case

is

where , always positive for melting, is the latent heat of fusion and is the change in volume during the phase change. If the volume increases during melting, the most common circumstances, then the slope ⁄ is positive. If the volume decreases during melting, as in the case of water, the slope is negative. The same equation is applicable to the sublimation process (solid-vapor). If the pressure during vaporization is low enough, the vapor behaves nearly as an ideal ⁄ , which gas. If the volume of liquid is negligible compared with , then substituted into (4.2) gives an equation for which the volume data are not needed,

( rearranging gives us ( )(

) )

an equation, also called the Clapeyron equation, that gives reasonably accurate values of the latent heat at low pressures. This equation may perhaps be useful at pressures below those given in tables of properties.

5. General Relations for

.

In this section we develop we develop relations for changes in internal energy, enthalpy and entropy in terms of pressure, specific volume, temperature, and specific heats alone. We also develop some general relations involving specific heats which will enable us to determine the changes in these properties. Change in Internal Energy: We choose internal energy to be a function of T and v, that is

( we know that

)

(

) ( )

substituting

to (5.1) yields: ( )

Now we choose entropy to be a function of T and v; that is

( substituting

)

(

)

to (5.3) yields: ( ( ( ) ) ) ( [ ( ) ) ] ( )

equating the coefficients of dv and dT of (5.2) and (5.4) yields: ( ( ) ) ( )

using the Maxwell relation III on (5.6) yields: ( ) ( )

substituting this to (5.2), we obtain the desired relation for du: [ ( ) ]

The change in internal energy of a simple compressible system associated with a change of state from to is determined y integration: ∫ ∫ [ ( ) ]

Change in Enthalpy: We choose enthalpy to be a function of T and p, that is

( we know:

)

(

)

( substituting to (5.9) yields: ( )

)

Now we choose entropy to be a function of T and p; that is

( substituting

)

(

)

to (5.11) yields: ( ( ) ) ( ) ( )

(

)

* (

)

+

equating the coefficients of dT and dp of (5.10) and (5.12) yields: ( ( ) ) ( )

using the Maxwell relation IV on (5.14) yields: ( ) ( )

substituting this to (5.10), we obtain the desired relation for dh: * ( ) +

The change in enthalpy of a simple compressible system associated with a change of state from to is determined y integration: ∫ ∫ * ( ) +

In reality, one needs only to determine either from (5.8) or from (5.16), depending on which is more suitable to the data at hand. The other can easily be determined by using the definition of enthalpy :

Change in Entropy: Below we develop two general relations for the entropy change of a simple compressible system. The first relation is obtained by replacing the coefficients of dT and dv of (5.3) with (5.5) and Maxwell relation III, respectively, yielding ( and ∫ ∫ ( ) )

The second relation is obtained by replacing the coefficients of dT and dp of (5.11) with (5.13) and Maxwell relation IV, respectively, yielding ( and ∫ ∫ ( ) )

Either relation can be used to determine the entropy change, depending on the available data. Specific Heats and : The specific heats of an ideal gas depend on temperature only. For a general pure substance, however, the specific heats depend on specific volume or pressure as well as temperature. Below we develop some general relations to relate the specific heats of a substance to pressure, specific volume, and temperature. At low pressures gases behave as ideal gases, and their specific heats essentially depend on temperature only. Theses specific heats are called zero pressure, or ideal-gas, specific heats (denoted and ), and they are relatively easier to determine. Thus it is desirable to have some general relations that will enable us to calculate the specific heats at higher pressures from a knowledge of or and the p-v-T behavior of the substance. Such relations are obtained by applying the test for exactness to (5.18) and (5.20). Considering (5.18): ( applying the test for exactness yields: ( * ⁄ ( ) + ) ( * ( ) ⁄ ) + )

applying the test for exactness to (5.20) yields: ( ) ( )

The deviation of from with increasing pressure, for example, is determined by integrating (5.23) from zero to any pressure p along an isothermal path: ( ) ∫ ( )

This equation shows the deviation of specific heats of a real gas from an ideal gas at the same temperature. Another desirable relation involving specific heats is one that relates the two specific heats and . We start the development of such relations by equating the two ds relations (5.18) and (5.20) and solving for dT: ( ( ( ) ) ) ( ( ⁄ ) ) ( ⁄ ) ( )

choosing

and differentiating, we get ( ) ( )

equating the coefficients of either dv or dp of (5.25) and (5.26) yields ( ) ⁄ ⁄ ⁄ ( ) ( )

An alternative form of this equation is obtained by using the cyclic relation. We’ll start with the derivation of the reciprocity and cyclic relations. The function can also be expressed as if y and z are taken to be the independent variables. Then the exact differential of x is ( ) ( )

eliminate dx by combining (5.28) and (2.1a): ( ( *( rearranging yields: ( * for: * ( ) ( ( The reciprocity relation is: ⁄ for: *( ( The cyclic relation is: ( ) ( ) ( ) ) ( ) ( ) ) ( ) + ( ) ( ) ) + ) ( ) ( ) ( ) ) + *( *( ) ( ) ( ) ) ( ( ) + ) + ) *( ) ( ) ( ) ) ( ) ( ( ) ) ( + ( ( ) ( ) ) )

) ( ) +

) (

Replacing x, y, and z in (5.30) with p, v, and T, respectively, we can express the cyclic relation for an ideal gas ( rearranging yields: ( ) ( ) ( ) ) ( ) ( )

substituting this relation to (5.27) yields: ( ) * ( ( ) ) ( ( ) ) +

This relation can be expressed in terms of two other thermodynamic properties called the volume expansivity and the isothermal compressibility , which are defined as ( ( substituting these into (5.31), we get the third relation for ) ) called the Mayer relation:

Conclusions drawn from (5.34): 1. The isothermal compressibility is a positive quantity for all substances in all phases. The volume expansivity could be negative for some substances (such as liquid water below 4°C), but its square is always positive or zero. The temperature T in this relation is absolute, which is also positive. Therefore we conclude that the constant-pressure specific heat is always greater than or equal to the constant-volume specific heat:

2. The difference between zero.

and

approaches zero as the absolute temperature approaches

3. The two specific heats are identical for truly incompressible substances since v = constant. The difference between the two specific heats is very small and is usually disregarded for substances that are nearly incompressible, such as liquids and solids.

6. Joule-Thompson Coefficient. The pressure of a fluid as is passes through a restriction such as a valve, or a capillary tube always decreases. This process is known as throttling process, which occurs at constant enthalpy. During this process the temperature of a fluid may remain constant, increase, or decrease. Fig. 6.1 illustrates a throttling process of a fluid through an expansion valve.

The temperature behavior of a fluid during a throttling process is described by the JouleThompson coefficient, defined as ( Notice that if { temperature i temperature i decreases )

The Joule-Thompson coefficient also represents the slope of h = constant lines on a T-p diagram, shown in Fig. 6.2.

Some constant-enthalpy lines on the T-p diagram pass through a point of zero slope or zero Joule-Thompson coefficient. The line that passes through these points is called the inversion line, and the temperature at a point where a constant-enthalpy line intersects the inversion line is called the inversion temperature. The temperature at the intersection of the p = 0 line (ordinate) and the upper part of the inversion line is called the maximum inversion temperature. On the left side of the inversion line the slope of the constant-enthalpy line is positive, which means that . However, on the right side of the inversion line the slope of the constant-enthalpy line is negative, thus . Knowing the T-p diagram of a substance is important for refrigeration application. It is clear from this diagram that a cooling effect cannot be achieved by throttling unless the fluid is below its maximum inversion temperature. This presents a problem for substances whose maximum inversion temperature is well below room temperature. Next we develop a general relation for the Joule-Thompson coefficient in terms of the specific heats, pressure, specific volume, and temperature. This is accomplished by modifying the generalized relation for enthalpy change * ( ) +

For an h = constant process, dh = 0, then (5.15) becomes: * * * ( ( ( ) + ) + ) +

(

)

*

(

) +

which is the desired relation. Thus, the Joule-Thompson coefficient can be determined from knowledge of the constant-pressure specific heat and the p-v-T behavior or the substance. 7. The Δh, Δu, and Δs of Real Gases. We have mentioned several times that gases at low pressures behave as ideal gases. At high pressures, however, gases deviate considerably from ideal-gas behavior, and it becomes necessary to account for this deviation. Now we evaluate the changes in the enthalpy, internal energy, and entropy of real gases, using the general relations for du, dh, and ds developed earlier. Enthalpy Changes of Real Gases: The enthalpy of real gases in general depends on the pressure as well as on the temperature. The enthalpy change of a real gas during a process can be evaluated from the general relation for dh (Eq. 5.16). ∫ ∫ * ( ) +

where p1, T1 and p2, T2 are the pressures and temperatures of the gas at the initial and final states, respectively. For an isothermal process, dT = 0, and the first term vanishes. For an isobaric process, dp = 0, and the second term vanishes. Properties are point functions, and thus, the change in a property between two specified states is the same no matter which process path is followed. Consider for example the process shown in Fig. 7.1. The change in enthalpy in process 1-2 can also be analyzed using an alternative process 1-1*-2*-2. Although this increases the number of steps, it simplifies the integration of (5.16) since one property remains constant during each part of the process. The pressure p0 can be chosen to be very low or zero, so that the gas can be treated as an ideal gas during the p0 = constant process. Using a superscript asterisk (*) to denote an ideal-gas state, we can express the enthalpy change of a real gas during process 1-2 as

Using (5.16), the enthalpy change for process 1-1* can be expressed as ∫ * ( ) +

or ∫ * ( ) +

the first term on the right side of (5.16) vanishes because process 1-1* is a constant temperature process, that is, dT = 0.

For process 1*-2* the enthalpy change is ∫ For process 2*-2 the enthalpy change is ∫ * ( ) +

The difference between h and h* is called the enthalpy departure, and it represents the variation of the enthalpy of a gas with pressure at a fixed temperature. In computing for the enthalpy departure we can use the relation , where Z is the compressibility ⁄ into f F id l g Z f l g Z ≠ Fi w b i ⁄ :

(

)

*

+

since R & p are constants and Z & T are variables ( ( ) ) ( * ( ) ) +

substituting the above equation and ∫ , ∫ ,

⁄ to (7.2) yields: * ( ( ∫ ( ) ) ) +-

rearranging yields the enthalpy departure equation: ∫ ( )

This time we introduce two new dimensionless properties, reduced pressure pR and reduced temperature TR, which are defined as d where: pR = reduced pressure p = gas pressure pcr = critical pressure expressing (7.5) in terms of pR and TR yields: ∫ [ ]

TR = reduced temperature T = gas temperature Tcr = critical temperature

from calculus: ∫ since Tcr & pcr are constants, ( are zero, thus ∫ ∫ ∫ expressing this in terms of molar basis: *( ̅ ̅⁄ ̅ ) +⁄ ∫ ( ) ( ( ( ) ) ) )

where ̅ is the universal gas constant, M is the molar mass, and ̅ the enthalpy given on a molar basis. No we introduce a new property, enthalpy departure factor Zh, that is used to determine the deviation of the enthalpy of a gas at a given p and T from the enthalpy of an ideal gas at the same T. The values of Zh are presented graphical form as a function of pR and TR in a generalized enthalpy departure chart shown in Fig. 7.2. From the above equation Zh is presented as (̅ ̅ ̅ ) ∫ ( )

The equation for enthalpy departure factor can be used to simplify (7.1), where: d substituting these to (7.1) yields:

expressing this in molar basis yields: ̅ ̅ (̅ ̅ ) ̅

This simplifies the computation for the enthalpy change from 1-2 because values of Zh are ̅ ) can be determined using found in generalized enthalpy departure charts and ( ̅ ideal gas equations.

Internal Energy Changes of Real Gases: From the formula for enthalpy h = u + pv the change in internal energy can be determined.

substituting

d

yields:

expressing in molar basis: ̅ ̅ (̅ ̅ ) ̅

Entropy Changes of Real Gases: The entropy of an ideal gas depends on both pressure and temperature, which will provide some difficulty in deriving the equation for entropy change. The determination of entropy changes of real gases requires the use of the relation for ds derived earlier. ∫ ∫ ( )

In computing the change in entropy of real gases an alternative process path can also be used. The same concept used in deriving for the relations for the enthalpy changes is used here. However, for entropy change analysis, the alternative process path is more difficult compared to that of the enthalpy change shown earlier. The process path used in the analysis of entropy change is illustrated in Fig. 7.3. The entropy change can be expressed as

States 1 and 1* are identical ( and ) and so are states 2 and 2*. The gas is assumed to behave as an ideal gas at the imaginary states 1* and 2* as well as the

states between the two. Therefore, the entropy change during the process 1*-2* can be determined from the entropy-change relations for ideal gases. The computation of entropy change between an actual state and the corresponding imaginary ideal-gas state is more involved, however, and requires the use of generalized entropy departure charts. Now we derive the entropy departure using the isothermal process 1-a*-1* for illustration: referring to (5.21): ∫ ( ∫ ( ∫ *( substituting ⁄ and ⁄ : ∫ [( ∫ , ( ∫ * substituting and ̅ ̅ ̅ ⁄ ) * ( ( ( ) + ⁄ ) ] ) ) ) ( ∫ ( ∫ ( ) + ) )

)

) +-

and expressing in molar basis: ∫ * ( ) +

The difference ̅ ̅ is the entropy departure and Zs is the entropy departure factor. The values of Zs are presented in generalized entropy departure charts. To simplify computation for the entropy change during process 1-2 in Fig. 7.3 we can rewrite (7.9) as

or, in molar basis: ̅ ̅ ̅ ̅ ̅