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**• Some thermodynamic properties can be measured directly, but many others
**

cannot. Therefore, it is necessary to develop some relations between these two

groups so that the properties that cannot be measured directly can be evaluated.

The derivations are based on the fact that properties are point functions, and the

state of a simple, compressible system is completely specified by any two

independent, intensive properties.

• The equations that relate the partial derivatives of properties P, v, T, and s of a

simple compressible substance to each other are called the Maxwell relations.

They are obtained from the four Gibbs equations, expressed as

du Tds Pdv

dh Tds vdP

da sdT Pdv

dg sdT vdP

· −

· +

· − −

· − +

• The Maxwell relations are

s v

s P

T v

T P

T P

v s

T v

P s

s P

v T

s v

P T

∂ ∂

| ` | `

· −

∂ ∂

. , . ,

∂ ∂

| ` | `

·

∂ ∂

. , . ,

∂ ∂

| ` | `

·

∂ ∂

. , . ,

∂ ∂ | ` | `

· −

∂ ∂

. , . ,

• The Clapeyron equation enables us to determine the enthalpy change associated

with a phase change from knowledge of P, v, and T data alone. It is expressed a

sat

fg

fg

h

dP

dT Tv

| `

·

. ,

• For liquid-vapor and solid-vapor phase-change processes at low pressures, the

Clapeyron equation can be approximated as

2 2 1

1 1 2

sat sat

ln

fg

h

P T T

P R TT

| ` | `

−

≅

. , . ,

• The changes in internal energy, enthalpy, and entropy of a simple, compressible

substance can be expressed in terms of pressure, specific volume, temperature,

and specific heats alone as

v

v

p

P

v

v

p

P

P

du C dT T P dv

T

v

dh C dT v T dP

T

C P

ds dT dv

T T

C

v

ds dT dP

T T

]

∂

| `

· + −

]

∂

. ,

]

] ∂

| `

· + −

]

∂

. ,

]

∂

| `

· +

∂

. ,

∂

| `

· −

∂

. ,

• For specific heats, we have the following general relations:

2

2

2

2

v

T

v

p

T P

C P

T

v T

C

v

T

P T

| ` ∂ ∂

| `

·

∂ ∂

. ,

. ,

∂

| ` | ` ∂

· −

∂ ∂

. , . ,

2

, 0,

2

0

2

2

P

p T p T

P

p v

P T

p v

v

C C T dP

T

v P

C C T

T v

vT

C C

β

α

| ` ∂

− · −

∂

. ,

∂ ∂

| ` | `

− · −

∂ ∂

. , . ,

− ·

∫

where β is the volume expansivity and α is the isothermal compressibility, defined

as

1 1

and

P T

v v

v T v P

β α

∂ ∂

| ` | `

· · −

∂ ∂

. , . ,

• The difference C

p

– C

v

is equal to R for ideal gases and to zero for incompressible

substances.

• The temperature behavior of a fluid during a throttling (h = constant) process is

described by the Joule-Thomson coefficient, defined as

JT

h

T

P

µ

∂

| `

·

∂

. ,

The Joule-Thomson coefficient is a measure of the change in temperature of a

substance with pressure during a constant-enthalpy process, and it can also be

expressed as

JT

1

P p

v

v T

C T

µ

]

∂

| `

· − −

]

∂

. ,

]

• The enthalpy, internal energy, and entropy changes of real gases can be

determined accurately by utilizing generalized enthalpy or entropy departure

charts to account for the deviation from the ideal-gas behavior by using the

following relations:

( ) ( )

( )

( )

( )

( )

2 1

2 1

2 1 2 1 u cr

ideal

2 1 2 1 u 2 2 1 1

2 1 2 1 u

ideal

h h

s s

h h h h R T Z Z

u u h h R Z T Z T

s s s s R Z Z

− · − − −

− · − − −

− · − − −

where the values of Z

h

and Z

S

are determined from the generalized charts.

and specific heats alone as ∂P − P dv du = Cv dT + T ∂T v ∂v dh = C p dT + v − T dP ∂T P C ∂P ds = v dT + dv T ∂T v ds = • Cp ∂v dT − dP ∂T P T For specific heats. specific volume. the Clapeyron equation can be approximated as h fg T2 − T1 P2 ln ≅ R T1T2 sat 1 P sat • The changes in internal energy.• For liquid-vapor and solid-vapor phase-change processes at low pressures. enthalpy. and entropy of a simple. compressible substance can be expressed in terms of pressure. temperature. we have the following general relations: ∂2 P ∂Cv =T 2 ∂v T ∂T v ∂ 2v ∂C p = −T 2 ∂P T ∂T P .

defined as 1 ∂v β= v ∂T P • • 1 ∂v and α = − v ∂P T The difference Cp – Cv is equal to R for ideal gases and to zero for incompressible substances. and it can also be expressed as µ JT = − • 1 Cp ∂v v −T ∂T P The enthalpy. and entropy changes of real gases can be determined accurately by utilizing generalized enthalpy or entropy departure charts to account for the deviation from the ideal-gas behavior by using the following relations: .C p . internal energy. defined as ∂T µ JT = ∂P h The Joule-Thomson coefficient is a measure of the change in temperature of a substance with pressure during a constant-enthalpy process. The temperature behavior of a fluid during a throttling (h = constant) process is described by the Joule-Thomson coefficient.T ∂ 2v = −T ∫ 2 dP ∂T P 0 P 2 ∂v ∂P C p − Cv = −T ∂T P ∂v T vT β 2 C p − Cv = α where β is the volume expansivity and α is the isothermal compressibility.T − C p 0.

.u2 − u1 = ( h2 − h1 ) − Ru ( Z 2T2 − Z1T1 ) s2 − s1 = ( s2 − s1 )ideal − Ru Z s2 − Z s1 h2 − h1 = ( h2 − h1 ) ideal − RuTcr Z h2 − Z h1 ( ) ( ) where the values of Zh and ZS are determined from the generalized charts.

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