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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.
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
&
Now combine the expressions for dx and dz.
Rearranging,
or
Chain rule
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
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
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
dP
dT
sat
sat , 45 C
50o C 40o C
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
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
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)
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
s
T
s
T
v
P
v 1 s
P
T
v T
v
Cv
v
P T
T
P
v
P
u u2 u1 Cv dT T
T
v
T
T2
v2
P dv
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
h
dh
h
dT
P
P
dP
T
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
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
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
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
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
RT
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
vb
v2
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
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 )
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
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II
% Error
100%
135.37 62.14
100%
135.37
54.1%
University of Gaziantep / Mechanical Engineering Department / Prof. Dr. M.Y. GUNDOGDU : ME 303 Thermodynamics II