Termodinamica Aplicada 2 Modo de Compatibilidad

B
TERMODINAMICA APLICADA GRUPO B CURSO 2010-11

JOS LUIS USERO GARCA. DEPARTAMENTO DE QUMICA FSICA. UNIVERSIDAD DE SALAMANCA
1
TERMODINMICA APLICADA TERMODINMICA APLICADA
2 CURSO
INGENIEROS QUMICOS
CURSO 20010-2011
Derivadas parciales
teoremas
( , , ) 0 F x y z =
( , ) x y z
y
x x
dx dy dz
y z
| c c |
= +
| |
c c . .
x y y x
d d d d
| | | c c c c | | |
| | | | |
y z
y c c . .
( , ) y x z
z x
y y
dy dx dz
x z
c c | |
= +
| |
c c . .
z x y z
y y
dx dx dz dz
y x z z
| | | |
= + +
| | | | |
c c c c . . . . \ .
x y z
x y x
y z z
| c c c | |
=
| | |
c c c . . .
1
z z
x y
y x
| c c |
=
| |
c c . .
1
x y z
x y z
y z x
| c c c | |
=
| | |
c c c . . .
DEPARTAMENTO DE QUMICA FSICA-TERMODINMICA APLICADA Jos Luis Usero; USAL 2006
2
( , ) x x y z =
y z
x x
dx dy dz Mdy Ndz
y z
| c c |
= + = +
| |
c c . . y z
M N
dz dy
z y
| c c |
=
| |
c c . .
RELACIONES DE MAXWELL
F. GIBBS ENTALPIA F. HELMHOLTZ E. INTERNA
dU=dQ+dW
dU=TdS-pdV
G=H-TS H=U+pV
dH=Vdp+TdS
A=U-TS
dA=-pdV-SdT dG=Vdp-SdT
3
p T
V S
S V
| |
| |
| |
|
. .
c c
=
c c
T V
p S
p S
| |
| |
| |
|
. .
c c
=
c c
p S
T V
T V
| |
| |
| |
|
. .
c c
=
c c
V S
T p
p T
| |
| |
| |
|
. .
c c
=
c c
U(T,p) H(T,p) S(T,p)
dp
S
dT
T
S
dS
|
|
.
|
c
c
+ |
.
|
c
c
= dp
H
dT
T
H
dH
|
|
.
|
c
c
+ |
.
|
c
c
=
U=H-pV
relaciones termodinmicas
Fluidos reales
dH=TdS+Vdp
p
p T
T p
|
.
c
|
. c
p
p T
T p
|
.
c
|
. c
p T
S v
p T
| c c |
=
| |
c c . .
Cp
T
H
p
= |
.
|
c
c
V
p
V
p
p
H
p
U
T T T
|
|
.
|
c
c
|
|
.
|
c
c
=
|
|
.
|
c
c
dp
T
V
dT
T
S
dS
p p
|
.
|
\
|
c
c
|
.
|
\
|
c
c
= dP
p
H
dT C dH
T
p |
|
.
|
\
|
c
c
+ =
T TP T
p
V
p
T
V
T
p
U
|
|
.
|
c
c
|
.
|
c
c
=
|
|
.
|
c
c
H
dH CpdT dp
| c
+
| Vd d
V
dT
S
T (
(
|
| c
|
| c
4
T
dH CpdT dp
p
= + =
|
c
.
Vdp dp
T
dT
T
T
p p
+
(
(

|
.
|
c
|
.
|
c
T
Cp
T
S
p
= |
.
|
c
c
p T
T
V
T V
P
H
|
.
|
c
c
= |
.
|
c
c
o = |
.
|
\
|
c
c
p
T
V
V
1
dp
T
V
dT
T
Cp
dS
p
|
.
|
\
|
c
c
=
dp
T
V
T V CpdT dH
p (
(
|
.
|
c
c
+ = k =
|
|
.
|
\
|
c
c
T
p
V
V
1
B
2
Fluidos reales
dV
S
dT
S
dS |
| c
|
| c
U U | c | c
U(T,V) S(T,V)
dV
V
dT
T
dS
T V
|
.
|
c
+ |
.
|
c
=
dV
V
U
dT
T
U
dU
T V
|
.
|
c
c
+ |
.
|
c
c
=
V T
T
p
V
S
|
.
|
c
c
= |
.
|
c
c
V V
S p
dS dT dV
T T
c c | |
= +
| |
c c . .
dV
V
U
dT C dU
T
V
|
.
|
c
c
+ =
V
V
C
T
U
= |
.
|
\
|
c
c
pdV dV
T
p
dT
T
S
T dV
V
U
dT C
V

)
`
|
.
|
\
|
c
c
+ |
.
|
\
|
c
c
= |
.
|
\
|
c
c
+
dU=TdS-pdV
5
T T V
V V T ) . \ c . \ c . \ c
T
C
T
S
V
V
= |
.
|
\
|
c
c
p
T
p
T
V
U
V T
|
.
|
c
c
= |
.
|
c
c
dV
T
p
dT
T
C
dS
V
V
|
.
|
\
|
c
c
+ =
V
V
p
dU C dT T p dV
T
( c |
= +
| (
c .
E.T.E.
Fluidos reales
p V
dT V dT p
dS C dp C dV
T T T T
c c | | | |
= = +
| |
c c \ . \ .
p v
dp
T
V
T dV
T
p
T
dT
|
.
|
\
|
c
c
+ |
.
|
\
|
c
c
p V
P v
T T T T
| |
c c \ . \ .
v p
p
C C
dT
=
dV
V
T
dp
p
T
dT
p v
|
.
|
\
|
c
c
+
|
|
.
|
\
|
c
c
=
v p
v p
T
p
T
V
T C C |
.
|
\
|
c
c
|
.
|
\
|
c
c
=
v p T
T
p
T
V
V
p
|
.
|
\
|
c
c
= |
.
|
\
|
c
c
|
.
|
\
|
c
c
2
V p | | c | | c
( )
( ) S
v
p
v
p
V
p
T
P
T
V
C
C
|
.
|
\
|
c
c
c
c
c
c
=
( )
S
T
v
p
V
p
P
V
C
C
|
.
|
\
|
c
c
c
c
=
|
.
|
\
|
c
c
K p
V
V
C
1
dS=0
6
p T
v p
T
V
V
p
T C C |
.
|
\
|
c
c
|
.
|
\
|
c
c
=
K
TV C C
v p
2
o
=
= =
|
.
|
\
|
c
c
|
.
\ c
=
S
S
T
v
p
K
K
p
V
V
p
V
C
C
1
Fluidos reales
=
|
|
.
|
\
|
c
c
T
p
p
C
p T
T
H
p
|
.
|
\
|
c
c
|
|
.
|
\
|
c
c
=
| | cC U | | c | | c
T p
p
H
T
|
|
.
|
\
|
c
c
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c
|
.
|
\
|
c
c
=
p p
T
V
T V
T
p p p
T
V
T
T
V
T
V
|
|
.
|
\
|
c
c
|
.
|
\
|
c
c
|
.
|
\
|
c
c
=
2
2
V
|
|
| c
2
= |
.
|
\
|
c
c
T
V
V
C
V T
T
U
V
|
.
|
\
|
c
c
|
.
|
\
|
c
c
=
T V
V
U
T
|
.
|
\
|
c
c
|
.
|
\
|
c
c
=
)
`
|
.
|
\
|
c
c
|
.
|
\
|
c
c
= p
T
p
T
T
V V
V
T
p
T
|
|
.
|
\
|
c
c
=
2
2
7
p
T
V
T
|
|
.
|
\
|
c
c
=
2
V . \
c
Fluidos reales
Funcin de Gibbs: G=H-TS
p
G
S
T
c | |
=
|
c \ .
dT
RT
G
dG
RT RT
G
d
2
1
=
( ) dT
RT
TS H
SdT Vdp
RT RT
G
d
2
1
=
dT
RT
H
dp
RT
V
RT
G
d
2
=
RT
G
V
|
|
|
| c
dG=Vdp-SdT
G
V
| | c
|
8
T
p
RT
RT |
|
|
.
\
c
=
p
T
RT
G
T
RT
H
|
|
|
.
|
\
|
c
c
=
T
V
p
=
|
c
\ .
B
3
Equilibrio de fases
G
o
G
|
Ln p
s
=A+B/T
P y T constantes; dG=Vdp-SdT=0
TROUTON
o|
o|
o|
o|
V T
H
V
S
dT
dp
s
A
A
=
A
A
=
RT
r
s
r
T
D C B A
p
=

+ + +
=
1
1
ln
6 3 5 , 1
t
t
t t t t
WAGNER
( )
rn
c
N
N
T
p
RT
H
=
A
930 , 0
013 , 1 ln 092 , 1
RIEDEL
dG
o
=dG
|
G
o
=G
|
C T
B
A p
s
+
= ln
ANTOINE
CLAPEYRON
s s
V dp S dT V dp S dT
o o | |
=
10 ~
A
N
N
RT
H
10,6 NO POLARES
12,3 POLARES ( MENOS
ORGNICAS)
9
p
RT
V V VAPOR = ~ A
|
|
.
|
\
|
= A
2 1
1
2
1 1
ln
T T
p
p
R
H
CLAUSIUS-
CLAPEYRON
38 , 0
1
2
1
2
1
1
|
|
.
|
\
|
=
A
A
r
r
T
T
H
H
WATSON
2
2
ln ln
+ + + + = ET DT T C
T
B
A p
sat
RIEDEL
Efecto joule
P
1
, P
2
CONSTANTES
2
1
0
1 2 1 1 2 2
0
V
V
W PdV PdV V P V P
dU dW
U U V P V P
= =
=
} }
dq = 0
P
1
P
1
P
2
P
2
V
1
V
2
10
2 1 1 1 2 2
2 2 2 1 1 1
2 1
U U V P V P
U V P U V P
H H
=
+ = +
=
Efecto joule
ESTRANGULAMIENTO
dp
T
V
T V dT C dH
p
p
|
.
|
\
|
c
c
+ =
dp
T
V
T V
C C
dH
dT
p p p
)
|
.
|
\
|
c
c
=
1
( ) 1
1
=
|
.
|
\
|
c
c
=
|
|
.
|
\
|
c
= = T
C
V
T
V
T V
C p
dT
p p p H
JT
o
dH=0
ESTRANGULAMIENTO
dV p
T
p
T dT C dU
V
V (
|
.
|
\
|
c
c
+ =
dV p
T
p
T
C C
dU
dT
V V V
(
|
.
|
\
|
c
c
=
1
(
|
.
|
\
|
c
c
= |
.
|
\
|
c
c
= p
T
p
T
C V
T
V V U
J
1
dU=0
EXPANSIN LIBRE
11
Efecto joule
Temperatura de inversin mxima
T
> 0
< 0
H=constante
Lnea de inversin
12
p
B
4
Propiedades residuales
2
M M
IDEAL
M
RESIDUAL
2
2 1
1
( , ,...) M M M dM x y A = =
}
ECUACIN DE
ESTADO
M=M
IDEAL
+M
RESIDUAL
13
( ) 1 = Z
p
RT
V
R
p R R R R
Z
dZ d
p
dp
+ =
p R
T Constante T Constante
( )
}
=
p R
p
dp
Z
RT
G
0
1 dT
RT
H
dp
RT
V
RT
G
d
R R R
2
=
}
|
.
|
\
|
c
c
=
p
P
R
p
dp
T
Z
T
RT
H
0
T
R
R
p
RT
G
RT
V
|
|
|
.
|
\
|
c
c
=
p
R
R
T
RT
G
T
RT
H
|
|
|
.
|
\
|
c
c
=
( ) Z Z
d
Z
RT
G
p R
ln 1 1
0
+ =
}

1
0
+ |
.
|
\
|
c
c
=
}
Z
d
T
Z
T
RT
H
p
P
R

14
( )
0 0
1
p p R
P
S Z dp dp
T Z
R T p p
c | |
=
|
c \ .
} }
p
RT
G
RT
H
R
S R R
R
=
RT
G
R
= | ln
Estados de referencia
1. ES UNA REFERENCIA
A. PUEDE NO TENER EXISTENCIA REAL A. PUEDE NO TENER EXISTENCIA REAL
B. HAY QUE MANTENERLA
2. EL QUE CONVENGA EN CADA CASO
A. Gas ideal a 1 bar (imaginario)
B. Gas ideal a p0
15
C.
3. ES FUNCION DE LA TEMPERATURA
FUGACIDAD
dG=Vdp-SdT
GAS IDEAL a T cte
FLUIDO REAL
( ) ( )
0
0
, ln
f
G p T G T RT
f
= +
T=CTE
V=RT/P
dG=Vdp=RTdp/p
( ) ( )
2
2 1
1
, , ln
p
G p T G p T RT
p
= +
( ) ( )
0
0
, , ln
p
G p T G p T RT
p
= +
16
( ) ( )
0
f
( ) ( )
0
0
, ln
p
G p T G T RT
p
= +
f p | =
0
f
a
f
=
B
5
Coeficiente de fugacidad
0 0
0 0
ln ln ln
f p
G G RT G RT RT
f f
| = + = + +
ln
IDEAL
G G RT | = +
ln
R IDEAL
G G G RT | = =
P R
G d
17
( )
0
ln 1 ; T constante
P R
G dp
Z
RT p
| = =
}
Coeficiente de fugacidad
fases condensadas
( )
0 0
1
ln ln 1
p p
f dp V
Z dp
p p RT p
|
| |
= = =
|
\ .
} }
p C
C S S
pS
V
f p Exp dp
RT
|
(
= (
(

}
0
1 1
ln
pS p C
pS
f V V
dp dp
p RT p RT p
| | | |
= +
| |
\ . \ .
} }
ln ln ln
p C S C
S S
pS
f f V p
dp
p p RT p
= +
}
p C
pS
V
Exp dp
RT
(
(
(

}
Factor de POYNTING
SI V
C
Constante
18
pS
ln ln
p C S C
S S
pS
f f V
dp
p p RT
= +
}
( )
C S p C
pS
V p p
V
Exp dp Exp
RT RT
( (
( ~ (
( (

}
SI V
C
Constante
correlaciones generalizadas
( )
0
1
P R
G dp
Z
RT p
=
}
;
;
c r c r
p p p dp p dp
T T T dT T dT
= =
= =
( )
0
0 0
1
P R
p
P P R
p
H Z dp
T
RT T p
S Z dp dp
T Z
R T p p
c |
=
|
c .
c |
=
|
c .
}
} }
;
c r c r
T T T dT T dT = =
( )
0
2
1
P R
r
r
c r
P R
r
r
dp G
T Z
RT p
dp H Z
T
=
| c
=
|
c
}
}
19
0
0
1
r
c r r
p
P R
r
r
r r
p
p
RT T p
dp S Z
T Z
R T p
|
c
.
(
| c
= + (
|
c
( .

}
}
correlaciones generalizadas
0 1
0 1
Z Z Z
Z Z Z
e = +
| | | c c c
( ) ( )
0 1
R R
R
C C C
G G
G
RT RT RT
e = +
r r r
p p p
Z Z Z
T T T
e
| | | c c c
= +
| | |
c c c
. . .
( ) ( )
0 1
0 0
0 1
2 2
0 0
1 1
P P R
r r
r r
c r r
P P R
r r
r r
dp dp G
T Z T Z
RT p p
dp dp H Z Z
T T
RT T p T p
e
e
= +
| | c c
=
| |
c c
. .
} }
} }
( ) ( )
( ) ( )
0 1
0 1
R R
R
R R
R
C C C
H H
H
RT RT RT
S S
S
R R R
e
e
= +
= +
R
20
0 0
0 1
0 1
0 0
1 1
c r r r r p p
P P R
r
r r
r r r p p
RT T p T p
dp S Z Z
T Z T Z
R T p T
e
c c
. .
( (
| | c c
= + + ( (
| |
c c
( ( . .

} }
( )
0 1
0 1
ln ln ln
R
C
G
RT
e
| | e |
| | |
= = +
=
B
6
ecuacin del virial
21
ecuaciones de estado
22
Coeficientes de fugacidad
ecuaciones de estado
23
Sistemas abiertos
balance de materia
vc
vc
e s es
dm
m m m m
d
- - - -
= = = A
e s es
dt
Flujo estacionario
Flujo unidimensional: homogneo y perpendicular a la superfcie
vc m Ac V
- -
= =
24
0 vc m
-
=
A
C
B
7
Sistemas abiertos
balance de energa
( )
( )
2
1
2
vc
es
es
d mu
u C zg m Q pv m W
dt
- - - -
( | | (
= A + + + A +
| (
(
\ .
( )
2
1
2
vc
es
d mu
h C zg m Q W
dt
- - -
( | |
= A + + + +
| (
\ .
( )
2
1
2
vc
es
d mu
h C zg m Q W
dt
- - -
( | |
+ A + + = +
| (
\ .
FLUJO ESTACIONARIO
25
es hm Q W
- - -
A = +
( )
0
vc
d mu
dt
=
2
1
2
es
h C zg m Q W
- - -
( | |
A + + = +
| (
\ .
FLUJO ESTACIONARIO
Sistemas abiertos
PROCESO REVERSIBLE
MXIMO TRABAJO PRODUCIDO
MNIMO TRABAJO CONSUMIDO
RENDIMIENTO:
TRABAJO PRODUCIDO
PROCESO REVERSIBLE Y ADIABTICO PROCESO ISOENTRPICO
26
TRABAJO ISOENTRPICO
TRABAJO ISOENTRPICO
TRABAJO CONSUMIDO
Sistemas abiertos
TURBINAS H=W
s S
W H
W H
q = =
COMPRESORES S S
W H
W H
q = =
BOMBAS Lquidos, V=V(p)Cte
dH
S
=Vdp W
S
=V(p
2
-p
1
)
S S
W H
W H
q = =
27
INTERCAMBIADORES DE CALOR
0 hm
-
A =
Formulas termodinmicas
(bridgman)
28
B
8
(bridgman)
29
(bridgman)
30

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B

TERMODINAMICA APLICADA GRUPO B CURSO 2010-11

DEPARTAMENTO DE QUMICA FSICA-TERMODINMICA APLICADA Jos Luis Usero; USAL 2006

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