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Introduction
In Thermodynamics I & II, we discussed the meaning of various fluid properties and how
to use them in solving thermodynamics problems. Some properties (T, P, V, m) can be
measured directly, but others (u, h, s) must be derived. The purpose of this chapter is to
develop the tools necessary to derive the unknown quantities from the measureable ones
i.e. thermodynamic property relations.
Mathematical Representation
The states of simple compressible substances are normally specified by two independent
variables, and other properties are written as a function of those two. In other words, for
three properties x, y, and z, we can write
= f (x, y)
z
dy
2.2.1
dz =
dx +
x y
dz = M dx + N dy
2.2.2
where
M=
, and
N=
dz = N dy
P
dv
dP =
dT +
T v
v T
and if we evaluate the change in pressure during a constant temperature process, then we
have
P
dv
dP =
v T
EXAMPLE:
Internal Energy
u
dv
du =
ds +
s v
v s
du = T ds P dv
u
=T
2.2.3
s v
and
u
= P
2.2.4
v s
properties z = f (x, y)
graphically as well as
mathematically. If we choose
P
Volume
Temperature
we define
as the slope
P
v along the isotherm.
If we write dz = Mdx + Ndy , then the following important relations can be derived (see
homework problem):
x
y
z
= 1
z x
x y
y z
The two relations above were based on z = f (x, y) , which represents a dependence of
one variable on two others. We can also derive some useful relations among groups of
four variables, with two still being independent (e.g. P, v, T, and s). Let w, x, y, and z be
our variables, and start with the relations x = f (w, y) , and y = f (w, z) .
dx =
dw
+
dy
dy =
dw +
dz
w y
w z
z w
dx =
dw
+
dz
z
w
dx =
dw +
dz
z w
w z
w y
w z
=1
w z w x w
2.3.1
x y
= 1
2.3.2
z z x x y
2.3.3
w z
w y
w z
y
z
=1
2.3.4
z w x w
By definition,
Also,
v s
u 1 v 2
s
u
= P , (2.2.4), we have
and finally,
P
P
2C
RP
= RT +
= RT
1+
Using
R = CP CV , and
, we have
c = RT
Maxwells Relations
Pressure, volume, temperature, and entropy could be considered the four most basic
thermodynamic state parameters, in the sense that work interactions are related to
pressure and volume (wrev = Pdv), and heat interactions are related to temperature and
entropy (qrev = Tds). Also, all four can be fixed experimentally. Using a set of isobars,
isochors, isotherms and adiabats on a Pv diagram, James Clerk Maxwell (1831-1879)
derived a set of equations relating derivatives of these four properties. Among other
things, these useful relations can be used to relate changes in entropy to measurable
properties.
Maxwells relations can be derived using calculus and the four energy functions internal
energy (u) , enthalpy (h u + Pv) , Helmholtz free energy ( f u Ts) , and Gibbs free
energy (g h Ts) , as follows:
du = Tds Pdv
Now we have four equations in the form of dz = Mdx + Ndy , and we can use 2.3.1 to
relate derivatives of M and N:
P
MR #1
v s
s v
T
=
v
MR #2
P s
s P
P
=
s
MR #3
T v
v T
MR #4
T P
P T
Keypoints:
P, T, and v can be measured, and s can be derived from the Maxwell Relations.
The LHS of #3 and #4 come directly from measurements, and could also be calculated
given an equation of state.
EXAMPLE:
Evaluation of Entropy
Lets take a closer look at how the Maxwell Relations help in the evaluation
of entropy. In other words, lets express changes in entropy in terms of the
measurable properties P, v, and T. (We will also need CP and CV.) We have
three possible pairs of independent variables to choose from: (P,v), (P,T),
and (v,T). Each pair has two partial derivatives of s associated with it, for
a total of six:
s
,
s
,
s
,
s
,
s
,
P v
v P
P T
T P
v T
T v
s
=
v
P T
T P
s
P
v T
T v
The 6th and 4th can be evaluated using 2.2.3 and 2.2.4:
u
u
T
=C
s v
s v
u
=T
s v
T
=
CV
s v
=
C
P
T P
s
T
=
V
T v
P v
P v
s
T
C
P
v P
T P
v P
T
v P
Keypoints:
EXAMPLE:
u = u(T )
u
=0
v T
u
in terms of P, v, and T. Since we know an
v T
v T
v s
s v
v T
u
=T
(2.2.3)
s v
= P
(2.2.4)
v
s
=
s
(MR #3)
v
T
= P +T
= P +T
= P + P = 0
v T
T v
Measurable Derivatives
By conducting experiments in which some property is fixed (e.g. use a constant volume
vessel, or an insulated container), and measuring the change in some other
property (P, T, or v) as heat is added or work is
dT
properties.
Qrev
System
(m,n)
C = Q
V
m dT V