7)

Resolução:

( ∂∂TH ) ( ∂T∂P ) ( ∂∂ PT ) =−1 M =( ∂∂TH )

P H T T

C .M (
∂H)
=−1 M =−(
∂T )
∂P ∂V
P JT JT
T P

C (∂T )
C =(
∂T )
−1 ∂ S ∂H
M = JT P
P T P

8)
Resolução:
2
RT a ( RTc ) 1 RTc
P= − ; a=27 ; b=
v−b Cv P 64 Pc 8 Pc

v2 v2 v2
RT a RT a
W =−∫ Pdv →W =−∫ − dv →W =−∫ dv−∫ dv
v1 v −b v 2 v1 v −b v
v1 2

av−2+1 av−1 −a
−2
av = = =
−2+ 1 −1 v

W =−( RTln ( v−b ) )− ( −av )

a v
W =−RTln ( v−b ) + ¿ v 2

v 1

[
W = −RTln ( v 2 −b ) +
a
v2 ][
− −RTln ( v 1−b ) +
a
v1 ]
RT a
P1= − 2
v 1−b v 1

( )
2
m3 . Pa
27 8,314 x 425,1 k
mol . k
a=
64 x 3,796 x 106 Pa
a=1,3882

1 8,314 m3 Pa 425,1 k
b= x x 6
8 mol . k 3,796 x 10 Pa
 −4
b=1,1638 x 10

a a
W =−RTln ( v 2−b ) + + RTln ( v 1−b ) −
v2 v1

RT a m3
P1 = − 2 → v 1=0,0038
v 1−b v 1 mol
3
RT a m
P1= − 2 → v 2=0,0017
v 1−b v 1 mol

1,3882 1,3
W =−8,314 x 382,58 x ln ( 0,0017−1,1638 x 10 )+ +8,314 x 382,58 x ln ( 0,0038−1,1638 x 10 )−
−4 −4
0,0017 0,0
3 3
W =−3,1808 x 10 (−6,4480 ) +816,5882+3,1808 x 10 (−5,6038 )−365,315 8
4 4
W =−2,0509 x 10 + 816,5882−1,7825 x 10 −365,315 8
J
W =313 5 , 2724
mol

du=CvdT T
[( ) ] ∂P
∂T v
−P dv , T =Cte

du= T
[( ) ]
∂P
∂T v
−P dv , → P1=
RT a
− →
v−b v 2
∂P
=
R
∂T v v−b ( )
du= T
[ R
−
RT
] a
− 2 dv
v−b v −b v

a
∫ d u=¿∫ v 2 dv → ∆ U =
−a v
¿ → ∆ U=a
v v
2

1
1 1
[
− → ∆ U=1,3882
v 1 v2 ] 1
−
1
0,0038 0,0017
¿ ( )
J
∆ U =−451,2724
mol
9)

a) I α

α¿ ( )
1 ∂v
v ∂T P

1 nR 1 nR P nR
α= x = x = x
v P nRT P nRT P
P
 1 1 −3 −1
α= → =3,354 x 10 K
T T 298,15 K

II β

β ¿− ( )
1 ∂v
v ∂P T

−1 nR −1 P nR
β= x = x x
nRT P2 nRT 1 P2
P
−1 −1
β= =−1 atm
P
III MJT=?
M T =−Cpxμ

M J T ¿− ( )
1 ∂H
Cp ∂ P T

d H=C p dT v −T
[ ( )] ∂v
∂T P
d P ,T =Cte

α= ( ) →( ∂T∂ v ) =α v
1 ∂v
v ∂T P P

dH =v −T (
∂T )
∂v
=v −T ( α v )=v ( 1−α T )
P

−v
M JT = (1−α T )
Cp

IV Cp-Cv=?
Cp−Cv=nR
dU =dq+ dw=dq−Pdv
A partir de U(T,v)

d U=CvdT ( ∂U
∂v )
dv
T

dU =( ) d T +(
∂v )
∂U ∂U
dv
∂T v T

dU =CvdT + (
∂v )
∂U
dv
T
A partir de H(T,P)

d H=( ∂∂HT ) dT +( ∂∂HP ) d P

P T

dH =CpdT +(
∂P )
∂H
dP
T

dU =dq−Pdv → dq=dH=CpdT
dU=dH

CvdT + ( ∂U
∂v )
dv=CpdT −Pdv ÷(∂T )
T
P

( ∂CvT ) ∂ T +( ∂U
P ∂v ) ( ∂v
∂T ) =(
T
Cp ∂T
∂T )P
−P (
∂T )
∂v
P P

Cv+ (
∂ v ) (∂T )
=Cp−P (
∂T )
∂U ∂v ∂v
T P P

Cp=Cv +
[ ( ) ]( )
∂U
∂v T
+P
∂v
∂T P

Para um gás ideal

( ∂∂Uv ) =0
T

nRT
Pv=nRT →
P
∂ v nR
=
∂T P
nR
Cp=Cv + P
P
Cp−Cv=nR

b)IV
T =Cte
Gás não ideal
nRT P nR
P= → =
v−nb T v−nb

( ∂∂Uv ) =T ( ∂∂TP ) −P
T v
( ) [ ]
2
∂U nR nRT n a
=T − +
∂v T v−nb v −nb v 2

( )
∂U
∂v T
−n2 a
= 2
v

Cp−Cv=
[( ) ] ( )
∂U
∂v T
+P
∂v
∂T P

( )( )
2 2
−n a nRT n a ∂v
Cp−Cv= + +
v2 v−nb v 2 ∂T P

( )
3
∂v Rv ( v−nb)
=
∂ T P R T v 3−2 an( v−nb)2

( Rv 3(v−nb)
)
2 2
−n a nRT n a
Cp−Cv= + +
v2 v−nb v 2 RTv 3−2 an( v−nb)2
2 3
nR T v
Cp−Cv= 3 2
RTv −2 an(v −nb)

10)
Mostre que:
Resolução:

( ∂∂ UP ) =0
T

dU =dQ −dW −¿

( ∂∂ UP ) =( ∂∂QP ) +( ∂∂WP )
T T T

dW =−Pdv−¿

( ∂∂WP ) =−P ( ∂∂ Pv )
T T

( ∂∂ UP ) =( ∂∂QP ) −(−P ( ∂∂ Pv ) )
T T T

( ∂∂ UP ) =( ∂∂QP ) + P ( ∂∂ Pv )
T T T

A T constante, Q=W; dQ=dW

( ∂∂ UP ) =−P ( ∂∂ Pv ) + P ( ∂∂ Pv )
T T T

( ∂∂ UP ) =0
T

( ∂∂ HP ) =0
T

H=U + Pv
dH =dU + dPv+dPv ÷¿

( ∂∂ HP ) =( ∂∂ UP ) + P ( ∂∂Pv ) +v ( ∂∂ PP )
T T T T

Para gás ideal

P . v=RT
RT
v=
P

( ∂∂ Pv )= −RT
P 2

∂H ∂U RT
= +v − 2 P
∂P ∂P P
∂H ∂U
=
∂P ∂P
dU =CvdT a T constante
dT =0
dU =CvdT =0

( ∂∂ HP ) = ∂0P =0
T

( ∂∂ HP ) =0( ∂∂ HP ) = ∂0P =0
T T

( ∂∂ HP ) =0
T