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(8.3-1a)
dH = TdS + VdP
(8.3-1b)
dA = SdT PdV
(8.3-1c)
dG = SdT + VdP
(8.3-1d)
z
x
z
y
dx +
y
dy = Mdx + Ndy
(8.3-2)
z
x
and N =
y
z
y
A useful property of exact differential is that the order of partial differentiation does not
matter. That is
z
y x
M
y
=
y
=
x
N
x
z
x y
(8.3-2)
x
(8.3-3)
y
=
S
P
S
(8.3-4a)
V
T
P
S
V
S
P
=
S
V
S
P
T
=
T
V
T
=
T
(8.3-4b)
(8.3-4c)
(8.3-4d)
P
The Maxwell relations can be used to calculate entropy from PVT data. The derivative
relations of equations (8.3-1a)(8.3-1d) then enable us to calculate U, H, A, and G. The
Maxwell relations can also be obtained from the diagram
H
S
T
A
T
V
=
S
P
S
The sign of the derivative is obtained from multiplication of the individual sign of each
variable in a group. For TVS the sign is ()()(+) = +, for PSV the sign is (+)(+)() = .
Similarly, for the other three Maxwell relations we have
P
H
S
T
A
=
S
V
S
P
T
H
S
T
A
T
P
8-10
S
V
=
T
H
S
T
A
S
P
=
T
V
T
Example 8.3-1.3 ---------------------------------------------------------------------------------One mole of propane gas is to be expanded from 0.001 m3 to 0.040 m3 while in contact with
a heating bath at 100oC. The expansion is not reversible. The heat extract from the bath is
600 J. Determine the work for the expansion using the Van der Waals equation of state.
P=
RT
a
2
v b
v
Solution ----------------------------------------------------------------------------------------From the first law we have u = q + w. Since the amount of heat transfer q is given (600
J/mol), we only need to evaluate u to find w.
We write u as a function of the independent variables T and v since the values of these two
variables are given in the problem
u = u ( T, v )
du =
u
T
dT +
v
u
v
dv
T
We need to express
u
v
u
v
dv
T
A
H
S
Koresky M.D., Engineering and Chemical Thermodynamics, Wiley, 2004, pg. 222
8-11
u
s
du =
ds +
v
u
v
d v = Td s P d v
s
Therefore
Ts Pv
v
du =
s
v
dv = T
T
P dv
T
H
S
T
A
S
V
=
T
P
T
s
P
=
, the change in internal energy can now
v T
T v
be expressed solely in terms of measurable properties:
du =
P
T
P dv
v
P
T
P dv
v
=
v
R
v b
P=
P
T
RT
a
2
v b
v
P =
v
a
v2
Hence
u =
0.04 m3
0.001m3
s
T
v
a
a
dv =
P dv =
3
2
0.001m v
v
0.04 m3
8-12
0.04 m3
0.001m3
27 ( RTc ) 2
27 (8.314 10 5 369.9) 2
=
= 9.3610-6 m6bar/mol
64 Pc
64
42.46
Therefore
u = 9.3610-6
1
1
= 91310-5 m3bar/mol
0.04 0.001
u = 913 J/mol
Example 8.3-2.4 ---------------------------------------------------------------------------------Propane at 350oC and 600 cm3/mol is expanded in an isentropic turbine. The exhaust
pressure is atmospheric. What is the exhaust temperature? PvT behavior has been fit to the
Van der Waals equation with a = 92105 [(atmcm6)/mol2] and b = 91 [cm3/mol]. Solve this
using T as v as the independent variables, that is s = s(T, v). The Van der Waals equation is
given as
P=
RT
a
2
v b
v
cp
R
Solution ----------------------------------------------------------------------------------------Since propane is expanded in an isentropic turbine, we can construct a path such that the sum
of s is zero.
Koresky M.D., Engineering and Chemical Thermodynamics, Wiley, 2004, pg. 245
8-13
T2, v2
s2
Ideal gas
s1
s = 0
T1, v1
T
ds =
Since s =
Q
T
s
T
dT +
v
1
T
=
v
s
v
dv
T
Q
T
=
v
cv
T
=
T
P
T
T
A
Therefore
ds =
cv
P
dT +
T
T
S
V
=
T
P
T
dv
v
P=
RT
a
2
vb
v
P
T
=
v
R
vb
s =
T2
T1
cv
dT +
T
v2
v1
R
dv = 0
vb
c
cv
= p 1 = 0.213 + 28.78510-3T 8.82410-6T2
R
R
v2 b
=0
v1 b
(E-1)
v2 b
v1 b
(E-1)
=0
RT2
82.06T2
=
= 82.06T2
1
P2
82.06T2 91
=0
509
(E-2)
We can use the following Matlab statements to solve the nonlinear equation
>> fun=inline('0.213*log(x/623.15) + 28.785e-3*(x -623.15) - 4.412e-6*(x^2 623.15^2)+log((82.06*x-91)/509)');
>> T2=fsolve(fun,500,optimset('Display','off'))
T2 =
448.2512
>>
The temperature of the exhaust from the turbine is 448.3oK.
8-15
Example 8.3-3.5 ---------------------------------------------------------------------------------Develop a general relationship for the change in temperature with respect to pressure at
constant entropy
T
P
s
T
=
P
cP
s
and
T
P
=
T
v
T
yields
P
T
T v
=
P s c P T P
v
R
=
T P P
Therefore,
T
RT 1
v
=
=
P s
P cP cP
(b) Show that for an ideal gas with constant cP, an isentropic expansion from state 1 and state
2 yields equation Pv k = const.
Separation of variables provides
T
R P
=
T
cP P
5
Koresky M.D., Engineering and Chemical Thermodynamics, Wiley, 2004, pg. 245
8-16
Integration provides
R
T
P c
ln 2 = ln 2 P
T1
P1
T2
P
= 2
T1
P1
R
cP
P2 v 2
P
= 2
P1v1
P1
P2
R
cP
v 2 = P1
R
cP
v1
where
1
R c P R cv 1
=
=
=
cP
cP
cP k
Pv k = const.
(c) Evaluate the expression for a gas that obeys the Van der Walls equation of state.
In Part (a), we found
T
T v
=
P s c P T P
Using the derivative inversion rule, we find for the van der Waals equation
P=
RT
a
2
vb
v
Rv 3 (v b )
v
=
T P RTv 3 2a(v b )2
Therefore,
T
1
RTv 3 (v b )
=
P s c P RTv 3 2a (v b )2
8-17