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# c 2011 Ismail Tosun

## Chapter 2 Thermodynamic Properties of Real Substances

Thermodynamics deals with the work and heat interactions of the system with its surroundings as it undergoes a process. These quantities can be estimated once the changes in various state functions, namely, internal energy, enthalpy, and entropy, are known. The purpose of this chapter is to develop general expressions to calculate changes in internal energy, enthalpy, and entropy. 2.1 WORK FUNCTIONS For a closed system undergoing a reversible isothermal process, integration of Eq. (1.6-8) gives Qrev = T S The use of Eq. (2.1-1) in Eq. (1.5-7) leads to U = T S + Wrev (2.1-2) (2.1-1)

in which the changes in kinetic and potential energies are considered negligible. Rearrangement of Eq. (2.1-2) results in Wrev = (U T S)

= A = Ainitial Af inal

(2.1-3)

where the term A is called the Helmholtz energy and is dened by A = U TS (2.1-4)

Since U , T , and S are all state functions, Helmholtz energy is a state function. It is also an extensive property. As can be seen from Eq. (2.1-3), the decrease in the Helmholtz energy indicates the maximum work that can be obtained from a closed system undergoing an isothermal process. The term A comes from the German word "Arbeit", meaning work. For a steady-state ow system undergoing a reversible isothermal process, combination of Eqs. (1.5-9) and (1.6-9) yields (2.1-5) H = T S + (Ws )rev in which the changes in kinetic and potential energies are considered negligible. Rearrangement of Eq. (2.1-5) gives (Ws )rev = (H T S)

= G = Ginitial Gf inal 11

(2.1-6)

where the term G is called the Gibbs1 energy and is dened by G = H TS (2.1-7)

Since H, T , and S are all state functions, Gibbs energy is a state function. It is also an extensive property. As can be seen from Eq. (2.1-6), the decrease in the Gibbs energy indicates the maximum work that can be obtained from a steady-state ow system under isothermal conditions. Helmholtz and Gibbs energies are sometimes referred to as work functions. Examination of Eqs. (2.1-4) and (2.1-7) indicates that A < U and G < H as a result of the subtraction of the term "T S". Hence, the term "T S" can be interpreted as a measure of unavailable energy. 2.2 THERMODYNAMIC PROPERTIES OF A SINGLE-PHASE SYSTEM 2.2.1 Fundamental Equations In dierential form, the rst law of thermodynamics for a closed system is given by dU = Q + W (2.2-1)

If the process is reversible, substitution of Eqs. (1.3-2) and (1.6-1) into Eq. (2.2-1) gives dU = T dS P dV The denition of enthalpy is given by H = U + PV The dierential form of Eq. (2.2-3) becomes dH = dU + P dV + V dP Substitution of Eq. (2.2-2) into Eq. (2.2-4) gives dH = T dS + V dP The denition of Helmholtz energy is given by A = U TS The dierential form of Eq. (2.2-6) becomes dA = dU T dS S dT Substitution of Eq. (2.2-2) into Eq. (2.2-7) gives dA = P dV S dT The denition of Gibbs energy is given by G = H TS
1

(2.2-2)

(2.2-3)

(2.2-4)

(2.2-5)

(2.2-6)

(2.2-7)

(2.2-8)

(2.2-9)

In honor of Josiah Willard Gibbs, professor of mathematical physics at Yale University. He was awarded the rst PhD degree in engineering in the USA.

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The dierential form of Eq. (2.2-9) becomes dG = dH T dS S dT Substitution of Eq. (2.2-5) into Eq. (2.2-10) gives dG = V dP S dT (2.2-11) (2.2-10)

It is also possible to express Eqs. (2.2-2), (2.2-5), (2.2-8), and (2.2-11) in terms of mass or molar quantities, i.e., b b b dU = T dS P dV b b b dH = T dS + V dP e e e dU = T dS P dV e e e dH = T dS + V dP (2.2-12) (2.2-13) (2.2-14) (2.2-15)

These equations are called fundamental equations. Note that fundamental equations consist of only properties and their dierential changes. These properties and their changes are state functions and are not dependent on the path or process involved. Therefore, once the initial and nal states are specied, the expressions given in Eqs. (2.2-12)-(2.2-15) hold for all processes (reversible or irreversible) and for a change of state in either a closed system or a steady-state ow system. 2.2.2 Maxwell Relations For an exact dierential, d, expressed in the form d = M (x, y) dx + N (x, y) dy the following relationship holds: M y N x (2.2-16)

b b b dA = P dV S dT b b b dG = V dP S dT

e e e dA = P dV S dT e e e dG = V dP S dT

(2.2-17)

Since internal energy, U , enthalpy, H, Helmholtz energy, A, and Gibbs energy, G, are all state functions, application of Eq. (2.2-17) to the expressions given in Eqs. (2.2-12)-(2.2-15) leads to P T = (2.2-18) e e e e V S S V T P =
e S

P T

e V T

e V

e V e S

(2.2-19)

e S e V

(2.2-20)

e S P

(2.2-21)

## These equations are known as the Maxwell relations.

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2.2.3 Internal Energy Change For a single-phase and single-component system, the Gibbs phase rule, Eq. (1.1-4), gives the number of degrees of freedom as two. Hence, the state of such a system is specied by two independent intensive properties. The dependence of internal energy on temperature and volume, i.e., e e U = U (T, V ) (2.2-22)

e e In order to express the term ( U / V )T in terms of measurable quantities, dierentiation of e Eq. (2.2-12) with respect to V keeping T constant gives ! ! e e S U =T P (2.2-24) e e V V
T T

leads to a convenient relationship to use in calculating the internal energy change2 . The total e dierential of U is given by ! ! e e U U e e dT + dV dU = T e e V T V ! e U e e dV (2.2-23) = CV dT + e V T

Thus, substitution of Eq. (2.2-25) into Eq. (2.2-23) gives the change in internal energy as e = CV dT + T P e e dU P dV T V e (2.2-26)

T

(2.2-25)

## The dependence of enthalpy on temperature and pressure, i.e., e e H = H(T, P ) (2.2-27)

leads to a convenient relationship to use in calculating the enthalpy change3 . The total diere ential of H is given by ! ! e e H H e dT + dP dH = T P P T ! e H e dP (2.2-28) = CP dT + P
T
2 3

e e e The functional form of internal energy can also be expressed as U = (P, T ) or U = (P, V ). e e e e The functional form of enthalpy can also be expressed as H = (T, V ) or H = (P, V ).

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## The use of Eq. (2.2-21) in Eq. (2.2-29) yields ! ! e e V H e =V T P T

T

e In order to express the term ( H/P )T in terms of measurable quantities, dierentiation of Eq. (2.2-13) with respect to P keeping T constant gives ! ! e e H S e =T +V (2.2-29) P P
T T

(2.2-30)

Thus, substitution of Eq. (2.2-30) into Eq. (2.2-28) gives the change in enthalpy as e e e dH = CP dT + V T 2.2.5 Entropy Change Before deriving the equations to calculate the change in entropy, it is necessary to express heat capacities at constant volume and pressure in terms of partial derivatives of entropy. e Heat capacity at constant volume, CV , is dened by ! e U e (2.2-32) CV = T e
V

"

e V T

! #
P

dP

(2.2-31)

e S T

(2.2-33)

P

e V

(2.2-34)

## The use of Eq. (2.2-13) in Eq. (2.2-34) leads to e CP = T

e S T

(2.2-35)

Entropy may be expressed as a function of temperature and volume, i.e., e e e S = S(T, V ) (2.2-36)

## e e The total dierential of S, dS, is given by ! ! e e S e e = S dT + dV dS T e e V

V T

(2.2-37)

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The use of Eqs. (2.2-20) and (2.2-33) in Eq. (2.2-37) gives the change in entropy as e e = CV dT + P e dS dV T T V e e e S = S(T, P ) (2.2-38)

It is also possible to express entropy as a function of temperature and pressure, i.e., (2.2-39)

The use of Eqs. (2.2-21) and (2.2-35) in Eq. (2.2-40) gives the change in entropy as e e CP dT dS = T Inverse rule The total dierential of the function f (x, y) is expressed as f f df = dx + dy x y y x e V T ! dP (2.2-41)

P T

(2.2-40)

## 2.2.6 Relationship Between Partial Derivatives

(2.2-42)

or

If both sides of Eq. (2.2-42) are dierentiated with respect to f by keeping y constant, the result is x f (2.2-43) 1= x y f y f x = 1 x f (2.2-44)

which is known as the inverse rule. Triple product rule Dierentiation of Eq. (2.2-42) with respect to y keeping f constant gives f f x 0= + x y y f y x The use of the inverse rule leads to 0= f x
y

(2.2-45)

x y

1 y f

(2.2-46)

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or

f x

x y

y f

= 1

(2.2-47)

which is known as the triple product rule. It can be memorized with a cyclic relation as shown in Figure 2.1, i.e., by marking the variables f , x, and y on a circle in the clockwise direction. Going in the clockwise direction, dierentiate one of the variables (let us call this the rst variable) with respect to the second one by keeping the third variable constant. Repeat this procedure for each of the variables going in the clockwise direction, and the product of three terms is equal to 1.
f x

Figure 2.1 Cyclic relation for the triple product rule. e Example 2.1 Evaluate ( V /T )P if a gas is represented by the following equation of state: P = Solution Since sible. triple RT a e e V b TV 2

e V cannot be expressed explicitly in terms of T and P , direct dierentiation is not pose Marking V , T , and P on a circle in the clockwise direction and the application of the product rule give
% V T

or

e V T e V T

!
P

T P

e V

P e V
e V

= 1

(1)

T P

With the help of the inverse rule, Eq. (2) takes the form ! (P/T )V e e V = T e (P/ V )
P T

P e V

(2)

(3)

P T

R e V b 17

e V

a e T 2V 2

(4)

## Substitution of Eqs. (4) and (5) into Eq. (3) yields e V T ! R e V b RT

P e V

RT e (V b)2 +

2a e e (V b)2 T V 3

a e T 2V 2

2a e T V3

(5)

(6)

2.2.7 Relationship Between Heat Capacities Dierentiation of Eq. (2.2-41) with respect to temperature keeping volume constant gives ! ! e e e V S P CP = (2.2-48) T e T T T V e
V P

e e e In general, it is dicult to express V as an explicit function of T and P , i.e., V = V (T, P )4 . It is e and T , i.e., P = P (V , T ). Therefore, the e much easier to express P as an explicit function of V e quantity ( V /T )P in Eq. (2.2-49) is dicult to evaluate and must be replaced by (P/T )V e e )T . From Eq. (3) of Example 2.1 and (P/ V ! (P/T )V e e V = (2.2-50) T e (P/ V )T P e e CP = CV T (P/T )2 e V (2.2-51)

## The use of Eq. (2.2-33) in Eq. (2.2-48) leads to ! e V P e eP = CV + T C T T V e

P

(2.2-49)

Substitution of Eq. (2.2-50) into Eq. (2.2-49) leads to the following relationship between heat capacities: e (P/ V )T

2.2.8 Coecient of Thermal Expansion and Isothermal Compressibility Coecient of thermal expansion, , is the variation of volume with temperature at constant pressure per unit volume, i.e., ! ! b e 1 V 1 V = = (2.2-52) b T e T V V
P P

## b Since = 1/V , it is also possible to express in terms of density as 1 = T P

4

(2.2-53)

The reason for this statement will be apparent in the next chapter.

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For most liquids, density increases with decreasing temperature. As a result, > 0. However, for liquid water between 4 C and 0 C, turns out to be negative. This is the reason why lakes start freezing from top to bottom. Isothermal compressibility, , is the variation of volume with pressure at constant temperature per unit volume, i.e., 1 = b V b V P ! 1 = e V e V P ! (2.2-54)

b Since volume decreases with increasing pressure, ( V /P )T is a negative quantity. To make positive, a minus sign is used in Eq. (2.2-54). In terms of density, Eq. (2.2-54) becomes 1 (2.2-55) = P T Both and remain almost constant for liquids and solids5 . Thus, as will be shown in the next chapter, coecient of thermal expansion and isothermal compressibility are especially useful in calculating changes in internal energy, enthalpy, and entropy for liquids and solids. Example 2.2 A 1 liter bottle is completely lled with an equimolar mixture of benzene and cyclohexane at 298 K. What pressure will develop within the bottle if it is heated to 305 K as a result of the sunlight coming through the lab window? The following data are provided for an equimolar mixture of benzene and cyclohexane: = 1.21 103 K1 Solution It is required to determine the variation of pressure with temperature at constant volume, i.e., (P/T )V . From the triple product rule T V P = 1 T V V P P T Solving for (P/T )V gives P T = 1
P

and

## = 108 106 bar1

T V

V P

=
T

(V /T )P (V /P )T

(1)

Assuming and to be constants, and the initial pressure within the bottle to be 1 bar, integration of Eq. (1) gives 1.21 103 (305 298) = 79.4 bar P =1+ 108 106 Comment: The bottle probably breaks before the pressure reaches 79.4 bar.

## This statement does not hold near the critical point.

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Example 2.3 At 573 K, the variation in the specic volume of steam as a function of pressure is given as follows: P ( MPa) 0.8 1.0 1.2 b V ( m3 / kg) 0.3241 0.2579 0.2138

a) Calculate the isothermal compressibility for steam at 1 MPa and 573 K. b) Compare this value with the one obtained by assuming that the steam obeys the ideal gas equation of state. Solution a) From Eq. (2.2-54) ! ! b b 1 V 0.2138 0.3241 1 V 1 = = 1.07 MPa1 ' = 0.2579 1.2 0.8 b P b P V V
T

e V P

RT P2

(1)

## Substitution of Eq. (1) into Eq. (2.2-54) gives ! e RT 1 P 1 V 2 = = 1 MPa1 = = RT P P e P V

T

So far, the equations developed to calculate changes in internal energy, enthalpy, and entropy apply to all substances. However, they contain partial derivatives involving T , P , and e V . Thus, an equation of state must be known for a substance in question. The following example shows how to evaluate the partial derivatives to determine changes in internal energy or enthalpy once the equation of state is known. Determination of changes in internal energy, enthalpy, and entropy for various equations of state will be covered in detail in the next chapter. Example 2.4 A piston-cylinder assembly contains 2 moles of a gas at 5 bar and 350 K. As a result of irreversible operations 3.5 kJ of work is done on the system, the nal pressure and temperature being 25 bar and 400 K, respectively. Calculate the heat interaction of the gas with the surroundings. Data: The gas obeys the following equation of state e P (V b) = RT e CP = 8.314 + 0.108 T 20

## e where CP is in J/ mol. K and T is in K.

Solution System: Contents of the cylinder When changes in kinetic and potential energies are negligible, the rst law of thermodynamics, i.e., Eq. (1.5-7), reduces to U = Q + W (1) Determination of Q requires the value of U to be known. The variation in internal energy can be determined from Eq. (2.2-26), i.e., e e = CV dT + T P e P dV (2) dU T V e From the given equation of state, RT P = e V b T and Eq. (2) simplies to P T
e V

P T

R e V b

(3)

## Therefore, the term

e V

P = Z

in which subscripts 1 and 2 represent the initial and nal states, respectively. To determine e CV , we have to use Eq. (2.2-51), i.e., e e CP = CV T R e V b e (P/ V )T P e V
T

e U =

RT RT =0 e e V b V b
T2

(4)

T1

e CV dT

(5)

(P/T )2 e
V

(6)

Note that

P T

e V

RT e (V b)2

(7)

(8)

Thus

## e CV = 8.314 + 0.108 T 8.314 = 0.108 T

(9)

Therefore, the heat interaction of the system with the surroundings is calculated from Eq. (1) as Q = U W = (2)(2025) 3500 = 550 J indicating that heat is added to the system.

## i 0.108 h (400)2 (350)2 = 2025 J/ mol 2

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Alternate solution: The change in enthalpy is given by Eq. (2.2-31), i.e., " ! # e V e e e dH = CP dT + V T dP T
P

(10)

## From the given equation of state,

or

Substitution of Eq. (11) into Eq. (10) and integration yield Z T2 e= e H CP dT + b (P2 P1 )
T1

RT e V =b+ P

e V T

R P

(11)

(12)

e e e Since U = H P V , the change in internal energy is given by From the given equation of state e e e U = H (P V ) e P V = RT + bP

e H = (8.314) (400350)+

i h i 0.108 h (400)2 (350)2 +4105 (25 5) 105 = 2520.7 J/ mol 2 (13) (14)

## Garvin, J., 2002, Chemical Engineering Progress 98 (7), 64-65.

PROBLEMS Problems related to Section 2.2 2.1 For steady-state ow through a throttling valve with negligible changes in kinetic and potential energies, the rst law states that the enthalpy remains constant, i.e., isenthalpic process. The variation of temperature with pressure in such a process is known as the JouleThomson coecient, . a) Show that the Joule-Thomson coecient is given by # " ! e V 1 e V T = T e C
P P

(1)

22

The throttling process may lead to an increase or decrease in temperature depending on the value of , i.e., >0 Temperature decreases on throttling (2) <0 Temperature increases on throttling The temperature at which the Joule-Thomson coecient changes sign is called an inversion temperature. At higher temperatures < 0, and at lower temperatures > 0. As a result, cryogenic applications require gas temperature to be lower than the inversion temperature. Most gases have an inversion temperature higher than room temperature. Hydrogen, however, has an inversion temperature of 80 C. In order to liquefy hydrogen, it is rst necessary to decrease its temperature below 80 C using liqueed nitrogen and then decrease its pressure by a throttling process. b) Show that the inversion condition, = 0, is given by the equation P e P +V =0 T T V e e V T c) Consider a gas obeying an equation of state of the form P = a RT e e V b V2

(3)

(4)

e e where a and b are constants. Assuming (V b)/V ' 1, show that the inversion temperature, Tinv , is approximated as 2a (5) Tinv ' Rb Although the inversion temperature turns out to be independent of pressure for this specic case, it is generally dependent on pressure. 2.2 Ammonia at 400 K and 5 MPa enters a throttling valve and leaves it at 100 kPa. Determine the exit temperature if the equation of state is given by e P (V b) = RT

where b = 3.73 105 m3 / mol. The molar heat capacity at constant pressure is given by e where CP is in J/ mol. K and T is in K. (Answer: 404.7 K) e CP = 25.895 + 0.033 T

The gas is compressed irreversibly and isothermally from an initial pressure of P1 to a nal pressure of P2 . a) Use Eq. (2.2-31) and show that e = a 2 b (P2 P1 ) H T 23 (2)

(1)

## b) Using the identity show that

e e e U = H (P V ) e U = b(P1 P2 ) T

(3)

(4)

## c) Use Eq. (2.2-26) to obtain

and show that the use of Eq. (1) in Eq. (5) leads to Eq. (4).

e U = bR

1 b e V2 a + T

b e V1 a + T

(5)

d) Show that the entropy change associated with this compression is given by P2 b(P1 P2 ) e = R ln S + P1 T2 P = where a = 35 J. K. m3 / mol2 RT a e e T V2 V b and

(6)

## 2.4 Consider a piston-cylinder assembly containing 3 moles of gas represented by

The gas expands irreversibly from 0.01 m3 to 0.02 m3 at 350 K. Use Eq. (2.2-38) and calculate the change in entropy associated with this process. (Answer: 17.6 J/ K) 2.5 a) Consider a function y = 3 x2 1 First evaluate dy/dx. Then express x as a function of y, i.e., r y+1 x= 3 and evaluate dx/dy. Conclude that dy 1 = dx dx/dy b) Consider a function y = 3 x2 sin x + ln x Show that x dx = 2 + 1 x cos x dy 6x z = 6x2 y Show that x y = 1 + ln x x

## b = 4.8 105 m3 / mol

c) Consider a function

6 x4 12 x3 x + 1

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2.6 Show that the ratio of the heat capacities is expressed in the form e T 2 CV =1 b e CP CP ( K1 )

b Using the following values at 298 K and 1 bar, evaluate the term T 2 /(CP ). Substance ( kg/ m3 ) 1000 8920 ( Pa1 ) Water Copper 2.5 104 5 105 4.53 1010 9.1 108 4186 386

b CP ( J/ kg. K)

e e Although it is widely assumed that CV ' CP for solids and incompressible liquids, this assumption is not generally correct for various liquids. For a more thorough discussion on the subject, see Garvin (2002). 2.7 Show that the Gibbs energy can be regarded as a generating function to estimate enthalpy, internal energy, Helmholtz energy, and heat capacity, i.e., ! e G e e H =GT T
P

e e U =GT e e A =GP e CP = T

e G T

e G P

e G P

e 2G T 2

2.8 Express the term (T /P )S in terms of measurable quantities as follows: e a) Use the triple product rule to show that e ( S/P )T T = P S e e ( S/T )
P

(1)

## b) Use Eq. (2.2-41) and conclude that ! ! e e V S = P T T P ! e e S CP = T T

P

(2)

(3)

c) Show that the substitution of Eqs. (2) and (3) into Eq. (1) leads to e T VT = P S e e CP 25

(4)

d) Also combine Eq. (4) with Eq. (1) of Problem 2.1 to obtain e) A gas obeying T P =+ e V (5)

e S

## (Answer: e) Decreases) 2.9 Show that a)

ows through an isentropic nozzle from high pressure to low pressure. Will the gas temperature decrease or increase? f ) If a solid is compressed adiabatically, show that the increase in temperature is given by P T = exp b CP

e P (V b) = RT

e CP

(6)

b)

c)

e G T

e H e V

T 1 e V e S = e CP T

= !

e H T

e V

e S

2.10 The volume of an aluminum sphere is reduced from 48.25 cm3 to 48.17 cm3 at 300 K by applying increased pressure. Use Eq. (2.2-38) and Eq. (1) of Example 2.2 to estimate the change in entropy. For aluminum = 6.9 105 K1 (Answer: 0.418 J/ K) 2.11 Changes in potential energy are considered negligible in the development of the fundamental equations, i.e., Eqs. (2.2-2), (2.2-5), (2.2-8), and (2.2-11). When the gravitational force is appreciable, the change in potential energy is represented by dEP = mg dz (1) and = 13.2 1012 Pa1

where m is the mass, g is the acceleration of gravity, and z is the distance measured in the direction opposite to gravity. Under these circumstances, show that the fundamental equations take the following form: dU = T dS P dV + mg dz (2) dH = T dS + V dP + mg dz 26 (3)

dA = P dV S dT + mg dz dG = V dP S dT + mg dz

(4) (5)

2.12 A closed system containing one mole of ethanol at 298 K and 1 bar receives 2700 J of heat from its surroundings. a) Calculate the nal temperature and pressure if heating takes place at constant volume. b) Calculate the nal temperature and molar volume if heating takes place at constant pressure. e Assume that CP , , and can be considered constant over the temperature ranges considered in this problem. Ethanol at 298 K and 1 bar exists in liquid form and has the following properties: e V = e CP = = = 58.39 cm3 / mol 112.4 J/ mol. K 1.12 103 K1 1.11 109 Pa1

(Answer: a) 327.1 K, 292 bar b) 322 K, 59.98 cm3 / mol) 2.13 Specic volume of liquids can be expressed as a function of temperature and pressure in the form b (P, T ) = V (0, T ) 1 C ln 1 + P b (1) V B(T ) which is known as the Tait equation. Show that the isothermal compressibility is given by = P + B(T ) P 1 ln 1 + C B(T ) 1 (2)

## a) Use the triple product rule to show that ! e V P

e S

2.14 Isentropic compressibility, , is the variation of volume with pressure at constant entropy per unit volume, i.e., ! e 1 V = (1) e P e V
S

V

e e ( S/ V )P

e ( S/P )V e

(2)

(3)

(4)

## d) Substitute Eqs. (3) and (4) into Eq. (2) to get ! e! e e V V CV T = P e P V T e e C P S

P

(5)

27

f ) Show that the use of Eq. (6) in Eq. (5) leads to = g) The speed of sound, u, is dened by u = Express Eq. (8) in the form
2

## e) Use the triple product rule to show that ! e! e T V V = P V T P e

P

(6)

e CV

e CP P

(7)

(8)

e V 2 P M V S e e where M is the molecular weight. Combine Eq. (9) with Eq. (1) to obtain u2 = = 1 u2

e S

(9)

(10)

Once the speed of sound and density are experimentally measured, the isentropic compressibility is calculated from Eq. (10).

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