TERMODINAMICA II

PROBLEMAS

1.-PROBLEMA 5.7. MODELL

Express the following in terms of Cp, P, V, T and derivatives of these variables

(a) ( ∂∂ TS )
G, N

SOLUCION:

Sabemos que

( ∂∂ TS ) =( ∂∂ TS )
G, N G

−(
T)
∂S

( ∂ T ) ∂ G … … … … … … .(α )
∂S
=
∂ G

G
(∂S ) T

De: ∂ G=V . ∂ P−S . ∂T derivando con respecto a T y S se obtiene

( ∂∂ TS ) =V ( ∂∂TP ) −S
G S
………………… (1)

( ∂∂ GS ) =V ( ∂∂ PS )
T T
……………..…… (2)

Reemplazando (1) Y (2) en (α)

( ∂P
)
S−V . V .(
∂T )
∂P

(∂T ) V . ∂ P V . ∂ P V . ∂P
∂S
=
∂ T
=
S
−
S S

( ∂ S ) ( ∂S ) ( ∂S )
G

T T T

De Maxwell: ( ∂ S ) =−( ∂ V ) y
∂P ∂T
T P

( ∂∂ TP ) =( ∂∂VS ) =( ∂∂TS ) ( ∂V∂T ) = T ( ∂∂VT )

Cp
S P P P P

Reemplazando:

( ∂∂TS ) = T − S (∂ VV/∂ T )
Cp
G

( )
T P
Cp
Siendo : S=S +∫ dT −∫ ( ∝¿¿ p V )T dT ¿
0

T
O T P
0
P
0
 TERMODINAMICA II

(b) ( ∂∂ GA )
G, N

SOLUCION

( ∂∂ GA ) =( ∂∂GA )
G,N G

( ∂∂ GA )=( ∂∂ AP ) ( ∂∂GP ) ………….(1)

T T

Sabemos que: ∂ A=P . ∂V -S.∂T derivando con respecto a T

( ∂∂ AP ) =−( ∂V
T ∂P ) −S (
T
∂T
∂P ) ( ∂A
∂P ) =−P (
T ∂P )
∂V
T
… (2)
T

∂ G=V . ∂ P -S. ∂ T derivando con respecto a T

( ∂∂ GP ) =V ( ∂∂ PP ) −S ( ∂∂ TP ) ( ∂∂ GP ) =V …(3)
T T T T

Reemplazando (2) y (3) en (1)

( ∂∂ GA )= V .(−P∂ P )
∂V T

k T=
−( ∂∂ VP ) T
V

( ∂∂ GA )=P . k T

2.-Problema 5.22 Modell:

a. Starting with the following alternative definition of Cp and Cv

C p=T ( ∂∂TS ) P

C V =T ( ∂∂TS ) V

Show that Cp−C V can be expressed as a function of PVT properties only. Using the
result of part a show that C p−C v =R for an idea gas.
 TERMODINAMICA II

Cp
b. Given that C P −CV =f ( P , V ,T ) from part a, is it posible to express the ratio k =
Cv
as an explicit function of PVT properties and their derivatives? Explain your answer.

Solución

Diferenciando S en función de T y V

∂ S ( T , V )= ( ∂∂TS ) dT +( ∂∂VS ) dV
V T

( ) dV
CV ∂S
∂ S ( T , V )= dT +
T ∂V T

Usando la relación de Maxwell: ( ∂∂ TP ) =( ∂∂VS )

V T

( ) dV
CV ∂P
∂ S= dT +
T ∂T V

Entonces

( ) ( ) ( )( ) ( ) ( ∂V∂T )
∂S C ∂T ∂P ∂V CV ∂ P
= V + = +
∂ T P T ∂T P ∂T V ∂T P T ∂T V P

( ) ( ∂∂VT )
CP CV ∂ P
= +
T T ∂T V P

C P −CV =T ( ∂∂TP ) ( ∂V
∂T )
V P

RT
Para un gas ideal: P=
V

C P =CV + ( PVR )( VR )( RP )
C P −CV =R

Para el caso de Cp/Cv,

CP CP
k= =
CV
C P−T ( ∂∂ TP ) ( ∂∂VT )
V P

Debido a que C p es función de la temperatura

2 3
C p (T )=a+bT + c T +d T
 TERMODINAMICA II

Por lo tanto, es posible expresar el coeficiente de dilatación adiabática, en términos de

PVT

3.-Problema 5.27 Modell

J
A non-ideal gas of constant heat capacity C v =12 .56 undergo a reversible
mol . K
adiabatic expansion. The gas is described by the Van der Waals equation of state

( P+ Va ) (V −b )=RT
2

3 3
Jm −5 m
Where a=0 . 1362 2 and b=3 . 215 x 10 .Derive an expression for the
mo l mol
temperature variation of the gas internal energy, and calculate its value when the
gas volumen of 400 moles is 0.1 m 3 and its temperature is 294K.

Solución

dU ( T ,V ) = ( ∂∂UT ) dT +( ∂∂UV ) dV
V T

De: dU =TdS−PdV

( ∂∂UT ) =T ( ∂∂TS ) −P ( ∂V
V ∂TV
) =T (
∂T )
∂S
V
=C
V
V

( ∂∂VU ) =T ( ∂V∂ S ) −P ( ∂∂ VV ) =T ( ∂V∂ S ) −P

T T T T

dU =C dT +[T (
∂V )
∂S
V −P]dV
T

De maxwell: (
∂V ) (∂T )
∂S ∂P
=
T V

dU =C dT +[T (
∂T )
∂P
V −P ]dV
V

De la ecuación de Van der Waals

( ∂∂ TP ) = V R−b − Va
V
2

dU =CV dT +
[ RT
−
RT a
+ 2 dV
V −b V −b V ]
a
dU =CV dT + dV
V2
Integrando
 TERMODINAMICA II

1 1
U −U 0=C V ( T −T 0 )−a ( − )
V V0

∆ U =12.56 ( 294−T 0 )−0.1362

( 0.11 − V1 ) 0

5.-Demostrar

T2
∆ H =∫ C P dT + H 2 −H 1
0 R R

T1

SOLUCIÓN:

( )
P2 T2 0

( ) ( ∂∂ HP )
0
∂H ∂H
∆ H =∫ dP+ ∫ dT +∫ dP
0 ∂P T=T 2 T1 ∂T P P1 T=T 1

Usando las relaciones de Maxwell y ecuaciones de gas ideal

( ∂∂ HP ) =−( ∂∂TP ) C
T H
P
0

dH =T . dS+ V . dP

( ∂∂ HP ) =T ( ∂∂ PS ) + V ( ∂∂ PP )
T T T

Tenemos

(( ) ) (( ) )
P2 T2 P1
∂H ∂H
∆ H =∫ T +V dP+ ∫ C P dT −∫ T
0
+V dP
0 ∂P T T1 0 ∂P T

T2
∆ H =∫ C P dT + H 2 −H 1
0 R R

T1

6.-Demostrar

T2
C P0
∆ H =∫
T1 T
dT −Rln
P2
P1
R
( )
R
+¿ S2 −S1 ¿

Solución

( ) dT +∫ ( ∂∂ SP )
P2 T2 0

( )
0
∂S ∂S
∆ S=∫ dP+ ∫ dP
0 ∂P T=T 2 T1 ∂T P P1 T =T 1

Usando las relaciones de Maxwell y ecuaciones de gas ideal

( ∂∂ SP ) =−( ∂∂ VT )
T P
 TERMODINAMICA II

( )
0 0
∂S CP
=
∂T P T
Tenemos:
P2 T2 0 P1
∆ S=−∫
0
( )
∂V
∂T P
C
dP+ ∫ P dT +∫
T1 T 0
∂V
∂T ( ) dP P

Sumando y restando los términos:

P2

∫ RP dP
0

P1

∫ RP dP
0

(( ) ) (( ) )
P2 T2 0 0
∆ S=−∫
0
∂V
∂T P
−
R
P T =T 2
dP−Rln
P2
+∫
CP
P1 T1 T ( )
dT −∫
P1
∂V
∂T P
−
R
P T =T 1
dP

T2 0
C
∆ H =∫ P dT −Rln
T1 T
P2
P1
+¿ S2R−S1R ¿ ( )

7.-Demostrar

( ∂∂ bc )= bc
SOLUCION:

( ∂∂ bc ) =( ∂∂Nb ) ( ∂∂Nc )
d ,e d, e d ,e

( ∂N)
∂b

(∂c ) ∂c
∂b
=
d ,e
……………(α)
(∂N ) d ,e

d ,e

SABEMOS QUE : b=bN

c=cN

( ∂∂ Nb ) =( ∂∂bNN )
d ,e d,e
=N ( ∂∂Nb ) d, e
+b ( ∂∂ NN ) d ,e
=¿b ……………(1)

( ∂∂Nc ) =( ∂∂CNN )
d ,e d ,e
=N ( ∂∂ CN ) d ,e
+b ( ∂∂ NN ) d ,e
=¿c ……………(2)
 TERMODINAMICA II

( ∂∂ bc ) d ,e
=
b
c