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Problem 1

The molar enthalpy of vaporization of water at 373.15 K and one atm.


vap = 40.7 kJ
is H
and the molar entropy of vaporization under
mol
J
the same conditions is S vap = 109
. Assume that these
molK
values stay constant.
vap at 373.15 K. Assuming the reversible
A) Calculate the value of G
heat exchange with the surroundings calculate the total entropy
change of the universe (system+surroundings.)
vap at 373.15 K
G
vap = H
vap T S vap
G
J
1 kJ
vap = (40.7 kJ ) (373.15 K)*(109
G
)(
)
mol
molK
1000 J
vap = 0.02665 kJ
G
mol
vap at 378.15 K. Assuming the reversible
B) Calculate the value of G
heat exchange with the surroundings calculate the total entropy
change of the universe (system+surroundings.)
vap at 378.15 K
G
vap = H
vap T S vap
G
J
1 kJ
vap = (40.7 kJ ) (378.15 K)*(109
G
)(
)
mol
molK
1000 J
vap = -0.51835 kJ
G
mol
vap at 368.15 K. Assuming the reversible
C) Calculate the value of G
heat exchange with the surroundings calculate the total entropy
change of the universe (system+surroundings.)
vap at 368.15 K
G
vap = H
vap T S vap
G
J
1 kJ
vap = (40.7 kJ ) (368.15 K)* (109
G
)(
)
mol
molK
1000 J
vap = 0.57165 kJ
G
mol
D) Is the change of entropy of the universe consistent with the change
of Gibbs energy in each of the cases a), b), c)?
In part a, the molar Gibbs energy of vaporization is close to zero
meaning that liquid and vapor water are in equilibrium. The transfer of
vap = 0,
one mole of liquid water vapor under these conditions is G
which also means its a reversible process. In part b, the result of the
molar Gibbs energy of vaporization is negative, meaning that the

formation of one mole of water vapor from one mole of liquid water is a
spontaneous process. In part c, the result of the molar Gibbs energy of
vaporization is positive, meaning that the formation of one mole of
water vapor from one mole of liquid water is not a spontaneous
process. Therefore the change in entropy of the universe is consistent
with the change of Gibbs energy in each case.
Problem 2
The fundamental equation for an ideal gas (using molar, intensive
quantities):
R
V C
S

U=C V T 0
exp
V 0
C V
Find from this equation:
A) Temperature and pressure as a function of entropy S and volume
V : T ( S , V ), P ( S , V ).

U
U

d U=Td
SPd
V =
d S +
d V
S V
V S

( ) ( )
V

( ) ( )

U
T ( S , V )=
S

V
V 0

R
C

( ) ( )

=T 0

U
P ( S , V ) =
=T 0 R exp
V S

( )

[(

T
T0

exp

V0

S
C V

( )
R
C V

( )( )

(
( V )

R
1
C V

A ( T , V )=U (T , V )T S(T , V )

B) Helmholtz energy
S ( T , V )=C V ln

S
C V

V 0
V

R
C V

)( )

( T , V )=C V T
U
A ( T , V )=U (T , V )T S(T , V )
R
T V 0 C
A ( T , V )=C V T T C V ln
T 0 V

[(

)( )

C) Pressure and entropy as functions of temperature T and volume


: P ( T , V ), S ( T , V ).
dA=Pd V S dT :


A
RT
P ( T , V )=
=

V T V

( )

[(

A
T
=C V ln
T V
T0

( )

S ( T , V )=

V 0
V

R
C V

)( )

Problem 3
Show that:

( ( ))

V
dP+C p dT
T P
dH=TdS+VdP
H
S
=T
=C p
. 1
T P
T P
dH= V T

( HP ) =T ( SP ) +V

( ) ( )

Maxwell Relation:

( PS ) =( V
T )
T

( HP ) =T ( VT ) +V
T

dH=TdS+VdP
dH=Equation 1+ Equation2
dH =

( TH ) dT +( HP ) dP
P

[ ( ) ]
[ ( )]

dH=c p dT + T

V
T

dH=c p dT + V T
V
T

( ( ))

dH = V T

+V dP

V
T

dP

dP+C p dT

Problem 4
Similar to the previous problem derive the differential of internal
energy as a function of T and V which would include
only CV and pVT data.
dU =TdSPdV
S
=T (
=C
( U
)
T
T )
V

S
=T (
P
( U
)
V
V )
T

Maxwell relation:
S
P
=
V T T V

( ) ( )

P
=T (
P
( U
)
V
T )
T

( UT ) dT +( UV ) dV

dU =

dU =CV dT + T

( PT ) P ] dV
V

P
(
( T ) P) dV +C dT

dU = T

Problem 5
Using Maxwell relations, find the pressure dependence of internal
U
energy
for:
V T
A) Ideal gas PV=nRT

( )

P
(
( T ) P) dV +C dT

dU = T

P
=P+T (
( U
)
V
T )
T

PV=nRT

( PT ) =nR/V
V

nR
=P+T
( U
)
V
V
T

=P+ P=0
( U
V )
T

B) Gas whose equation of state is

( PT ) = V Rb
V

P ( V b )=RT

RT
=P+
( U
)

V
V b
T

=P+ P=0
( U
V )
T

C) Gas with Redlich-Kwong equation of state:


RT
A
P=
1/ 2
V b T V (V + B)
R
+
( PT ) = V B
2T
V

U
V

3/ 2

V ( V + B)

P
(
( ) T ) P= 2T
=T

1 /2

3A
V ( V +B)

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