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You are on page 1of 24

Some thermodynamic properties such as P, T, V, and m can be measured directly, but many

others such as h, u, and s cannot be measured directly.

Therefore, it is necessary to develop some relations between these two groups so that the nonmeasurable properties 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.

A) Thermodynamic properties are continuous point functions and have exact differentials.

A property of a single component system may be written as general mathematical function z =

z(x,y). For instance, this function may be the pressure P = P(T,v). The total differential of z is

written as

where

Taking the partial derivative of M with respect to y and of N with respect to x yields

Since properties are continuous point functions and have exact differentials, the following is true

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

B) Now we develop two more important relations for partial derivativesthe reciprocity and the

cyclic relations. Consider the function z = z(x,y) expressed as x = x(y,z). The total differential of x is

&

Now combine the expressions for dx and dz.

Rearranging,

each other, the terms in each bracket

must be zero. Thus, we obtain the

reciprocity relation that shows that the

inverse of a partial derivative is equal

to its reciprocal.

or

relation.

Chain rule

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

10.2 The Maxwell Relations:

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. The first two of the Gibbs equations are those

resulting from the internal energy u and the enthalpy h. The second two Gibbs equations result from

the definitions of the Helmholtz function a and the Gibbs function g defined as

1) du T ds P dv

2) dh T ds v dP

a u Ts

da du T ds s dT

3) da s dT P dv

(1.b)

(1.a) u f s, v du u ds u dv u T ; u P

s v

v s

s v

v s

h

h

h

h

(2.a) h f s, P dh s ds P dP s T ; P v

(2.b)

a

a

a

a

a f T , v da

dT

dv

s;

P

(3.a)

T v

v T (3.b)

T v

v T

g

g

g

g

g f T , P dg

dT

dP

s;

v

T

P

T

P

(4.a)

g h Ts

dg dh T ds s dT

4) dg s dT v dP (Maxwell Relations)

(4.b)

Compare

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

10.3 The Clapeyron Equation:

The Clapeyron equation enables us to determine the enthalpy change associated with a phase

change, hfg, from knowledge of P, v, and T data alone.

Consider the third Maxwell relation;

During phase change, the pressure is the saturation pressure, which

depends on the temperature only and is independent of the specific

volume. That is Psat = f(Tsat). Therefore, the partial derivative

can be

expressed as a total derivative (dP/dT)sat, which is the slope of the

saturation curve on a P-T diagram at a specified state. This slope is

independent of the specific volume, and thus it can be treated as a

constant during the integration of the third Maxwell relation between two

saturation states at the same temperature. For an isothermal liquid-vapor

phase-change process, the integration yields

During the phase-change process, the

pressure also remains constant.

Therefore, from the enthalpy relation

equation expressed as :

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

Example: Using only P-v-T data, estimate the enthalpy of vaporization of water at

45oC. The enthalpy of vaporization is given by the Clapeyron equation as;

SOLN:

Using the P-v-T data from saturated steam

table for water 45oC

3

m

v fg (vg v f )@ 45o C (15.251 0.001010)

kg

m3

15.250

kg

dP

dT

sat

sat , 45 C

50o C 40o C

kPa

0.4965

10o K

K

dP

dT

h fg Tv fg

sat

m3

kPa kJ

(40

(45+ 273.15) K (15.250

)(0.4965

)

kg

K m3kPa

The actual value of hfg is 2394.0 kJ/kg. The Clapeyron equation approximation

kJ

2408.91

2371.1

is low by about 1 percent due to the approximation of the slope of the

kg

o

saturation curve at 45 C.

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

Clapeyron-Clausius Equation

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

approximation to the Clapeyron equation can be obtained by treating the vapor phase

as an ideal gas and neglecting the specific volume of the saturated liquid or solid phase

compared to that of the vapor phase. At low pressures;

v v

g

v fg v g

RT

vg

P

For small temperature intervals, hfg can be treated as a constant at some average

value. Then integrating this equation between two saturation states yields

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

Example: Determine the saturation pressure of water vapor at -600C using the data

available in steam tables.

SOLN:

Tables do not give Psat for temperatures less than -400C. But we can use the

Clapeyron-Clasius equation for that purpose as that;

P2

ln

P1

sat

hig T2 T1

R T2T1

sat

Where;

T2=-400C

P2=0.0129 kPa (wrt T2)

hig=2838.9 kJ/kg (wrt T2)

R=0.46152 kJ/kgK for steam

0.0129

ln

P1

P1

IF T1=-600CP1=?

sat

0.0129

P1 0.00109kPa

2.4744

e

2.4744

sat

(Psat at -600C)

10.4 Some thermodynamic relations involving h, u, and s:

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.

1) Consider internal energy expressed as a function of T and v : u=f(T,)

the specific heat at

constant volume

Relation 3.a

v

s

T

s

T

v

P

v 1 s

P

T

v T

v

Cv

v

P T

T

P

v

v

P

u u2 u1 Cv dT T

T

v

T

T2

v2

P dv

2) Consider enthalpy expressed as a function of T and P : h=f(T,P)

h

dh

h

dT

P

P

dP

T

h

S

T

S

T

P

v

P

v

S

T

CP

P

v

P

v

dh CP dT v T

dP

v

h h2 h1 C P dT v T

T

P

T

T2

P2

dP

3) Two parallel expressions can be derived for the change of s: s=f(T,P) & s=f(T,v)

s f T , P

s f T , v

s

s

ds

dT

dP

T P

P T

s

s

ds

dT dv

T v

v T

Maxwell Rel. 3.a

CP

v

ds dT

dP

T

T P

T

dT P v

s s2 s1 CP

dP

T P T P

T

2

Cv

P

ds dT

dv

T

T v

T

dT v P

s s2 s1 Cv

dv

T v T v

T

2

10.5 Some thermodynamic relations involving Cp and Cv:

1)

ds

CP

v

dT

T

T

CP / T

2)

ds

T T

Cv

P

dT

T

T

Cv / T

M

N

dP

2v

T

M

N

dv

v

C P

T T

Cv

2P

T

CP

C

v

P

dT

dP v dT

dv

T

T

T P

T v

T P / T v

T v / T P

T

dT

dv

dP dT

C P Cv

C P Cv

v

T P / T v

T v / T P

T

T

&

C P Cv

C P Cv

v P

P v

3) ds

v

C P Cv T

P T

v

T

T

P

Chain rule

v

P

v

T

dv

dP

v

v

P

Example: Show that Cv of an ideal gas does not depend upon specific volume.

Therefore, the specific heat at constant volume of an ideal gas is independent of specific

volume.

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

10.6 Volume Expansivity and Isothermal and Adiabatic Compressibility:

The volume expansivity coefficient, p is an indication of the change in volume that results from a

change in temperature while the pressure remains constant (i.e. p =f(T)).

1 V

p

V T

1 v

v T

The isothermal compressibility, T is an indication of the change in volume that results from a

change in pressure while the temperature remains constant (i.e. T =f(P)).

1 V

T

V P

1 v

v P

The adiabatic compressibility, s is an indication of the change in volume that results from a

change in pressure while the entropy remains constant (i.e. s =f(P)).

1 V

1 v

s

V P s

v P

Both p and T are thermodynamic properties of a substance, and for a simple compressible

substance are functions of two independent properties.

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

Example: Determine Cp Cv for ideal gases.

Solution:

v P

CP Cv T

T P v

1 vT P2

T p v

T

T v

2

RT

P

1 v

1 R

1

p

v T P v P T

1 v

1 RT

1

T

v P T

v

P2

P

v

1

vT

vT P2

T

C P Cv

1

T

P

Pv

R

T

The difference Cp Cv is equal to R for ideal gases and to zero for incompressible

substances (v = constant).

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

10.7 Variation of h, u, s, Cp, and Cv for the Ideal gases: Pv=RT

v

1) dh CP dT v T

P

2) du Cv dT T

3) ds

CP

v

dT

T

T

RT

R

dP

C

dT

dP dh CP dT

P

P

P

RT

R

P dv Cv dT T

dv du Cv dT

v

v

dP

CP

R

dT

dP

T

P

P

T

P

dT

dP

s s2 s1 C P

R

C Pav ln 2 R ln 2

T

P

T

P

T1

P1

4) ds

T2

Cv

P

dT

Cv

R

dT

dv

T

v

dv

v

T

v

dT v dv

s s2 s1 Cv

R

Cvav ln 2 R ln 2

T

v

T

v

T1

v1

T2

v

5) C P Cv T

RT

R 3T 2

R3

R

T

2 2 2 2 C P Cv R

v

P v

R

P

In discussing the accuracy of the ideal gas equation of state, we introduced the compressibility

factor, Z as a useful and important parameter in expressing the non-ideality of gases;

Pv

Z=1 always for an ideal gas

RT

Another useful parameter in describing the behavior of a real gas relative to the ideal gas is the

residual volume, ;

=0 always for an ideal gas

RT

J=0 always for an ideal gas

T

PC Critical pressure

TC Critical temperature

vC Critical specific volume

Table A.1 ENGEL

Table A.6 Von WYLEN

Pr

P

Re duced pressure

PC

Tr

T

Re duced temperature

TC

v

vr

Re duced specific volume

vC

Z from

Generalised

Compressibility Chart

Fig.A-30a&Fig.A-30b ENGEL

Fig.A.5 Von WYLEN

critical temperature.

A gas is a species above its critical

temperature at a pressure low enough for

the species to be more like a vapor than a

liquid.

species can coexist in two phases (liquid

and vapor) is the critical temperature of that

species, Tc and the corresponding pressure

is the critical pressure Pc.

A substance at Tc and Pc is said to be at its

critical state.

GENERALZED COMPRESSIBILITY CHART

10.9 Equations of state:

An equation of state is an analytical representation of P-v-T behavior of gases.

Many different eqn. of states have been developed in literature. Three well-known classifications of

eqn. of state can be identified as, namely, generalized, empirical, and theoretical.

1) The best known of generalized eqns. of state is also oldest, namely, the van der waals

equation(1873);

RT

a

vb

v2

Redlich and Kwong eqn. of state (1949) is more accurate than van der waals eqn. of state.

RT

a

v b v v b T 1 / 2

2) One of the best known empirical eqns. of state is the Beattie-Bridgeman equation (1928);

RT

2 3 4

v

v

v

v

3) A different approach to this problem is from the theoretical point of view. The theoretical eqn. of

state, which is derived from kinetic theory or statistical thermodynamics, is written here in the form

of a power series in reciprocal volume;

Pv

B (T ) C (T ) D (T )

1

..........

RT

v

v2

v3

University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II

Example: Propane gas flows steadily through a pipe. The inlet state is 407 K, 5.21

MPa, and the exit state is 370 K, 4.26 MPa. Determine the heat loss from the propane to

the surroundings per unit mass of propane.

Conservation of mass

1 m

2 m

Conservation of energy

E in E out

m 1h1 Q out m 2 h2

Q out m ( h1 h2 )

the real gas analysis and determine the heat transfer

per unit mass as

Pcr = 4.26 MPa, Cp0 = 1.6794 kJ/kgK.

T1 407 K

P

5.21 MPa

11

. , PR1 1

12

.

Tcr 370 K

Pcr 4.26 MPa

T

370 K

P

4.26 MPa

TR 2 2

10

. , PR 2 2

10

.

Tcr 370 K

Pcr 4.26 MPa

TR1

Zh1 145

. ,

Zh 2 2.5

If we assumed propane to be an ideal gas

is

% Error

qout , real

100%

135.37 62.14

100%

135.37

54.1%

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