Classical ThermodynamicsGeneralization to Any Fluid

Fundamental property relation

provides a general connection

between energy balance and entropy
balance

Thus, allowing us to know how one

variable change in relation to others

Type of thermodynamics properties

Measured properties
P, v, T, composition

Fundamental properties
u (from conservation of energy)
s (from directionality of nature)

Derived thermodynamic properties

h = u + Pv
a = u Ts
(Helmholz energy)
g = h Ts
(Gibbs energy)

The fundamental property relation

For closed system, du = q w

For reversible process,
Heat exchange, q= Tds
Work, w= Pdv
du = Tds Pdv

(Eq. 2.2.1)

h = u + Pv
dh = du + Pdv + vdP
dh = Tds Pdv + Pdv + vdP
dh = Tds + vdP

(Eq. 2.2.2)

a = u Ts
da = du Tds sdT
da = Tds Pdv Tds sdT
da = sdT Pdv

(Eq. 2.2.3)

g = h Ts
dg = dh Tds sdT
dg = Tds + vdP Tds sdT
dg = sdT + vdP

(Eq. 2.2.4)

Important mathematical tools for the

manipulation of derivatives
1.

Basic identities
1
s

T P T

s P

s
s

0 and
0
T s
T T

s
1
s T

2.

Expansion rule

u u ( s, v)
du u / s v ds u / v s dv

3.

Triple product rule

Suppose h h(T , P ), then
dh h / T P dT h / P T dP
At constant h, dh 0
h T h
0


T P P h P T
h
T

P T
h P
T

or

P
P h h

P
h T

4.

Chain rule
z
T

z
T
h
h

P
P h z

T h z h

T P h

1
P h h T T P

Maxwell relations

For constant composition systems, any state property can

be expressed in terms of any other two state properties.
exact differential

u = u (s,v)

du u / s v ds u / v s dv
Expansion Rule

From the fundamental property relationships:

du = Tds Pdv

Therefore,

T u / s v ,

P u / v s

Considering second derivatives,

2u
2u
u
u

sv vs s v s v v s v s
P T

s v v s

A similar derivation applied to each of the

thermodynamic functions yields the Maxwells
Relations:

du Tds Pdv

P / s v T / v s

dh Tds vdP

v / s P T / P s

da sdT Pdv

P / T v s / v T

dg sdT vdP

v / T P s / P T

Example 1: Entropy change vs. T at constant P

Evaluate s/T P in terms of c p and T
Solution :
dh Tds vdP
If P is constant, then dP 0. Dividing through by dT,
h
s

T P
T P
h
The definition of c p is : c p

T P
cp
s
Therefore,

T P T

Example 2: Entropy change vs. T at constant v

Evaluate s/T v in terms of c v , T, P and v
Solution :
du Tds - Pdv
If v is constant, then dv 0. Dividing through by dT,
u
s

T v
T v
u
The definition of c v is : cv

T v
s cv
Therefore,

T v T

Example 3: Entropy change as a function of T and P

Derive a general relation for entropy changes of any fluid
with respect to temperature and pressure in terms of c p ,
P, v, T and their derivatives.
ds s / T P dT s / P T dP
But s / T P cP / T as derived in example 1,
and Maxwell's Relations show that s / P T v / T P .
ds (T , P) cP dT / T v / T P dP

(useful expression)

Some other useful expressions:

ds (T , v) cv dT / T P / T v dv
ds ( P, v) cv T / P v dP / T c p T / v P dv / T
dh(T , P ) c p dT v T v / T P dP
du (T , v) cv dT T P / T v P dv

Two measurable derivatives are commonly used

to discuss fluid properties:
T

1 v
1


v P T P T
1 v
1

v T P T P

isothermal compressibility
isobaric coefficient of thermal expansion

The
importance
manipulations

of

derivative

What is so important about the variables cp, cv, P, v, T?

As a sample application, we can assume the ideal gas
equation of state.

v RT / P

v / T P R / P

From the example 3,

ds(T , P ) c p dT / T v / T p dP
ds c p dT / T ( R / P )dP
s c p ln T2 / T1 R ln P2 / P1
(entropy change for an ideal gas)

Example 4: Entropy change for

ideal gas

Evaluate for an ideal gas that

ds ( T , P ) c p dT / T v / T

p dP

Example 5: Entropy change for a

simple non-ideal gas

Derive the pressure and temperature dependence of

entropy for a fluid that follows the simple equation of
state (EOS):
v= RT/P+(a+bT), where a and b are constants.

Hints on manipulating partial derivatives

Derivatives involve (s/T)v
and (s/T)P

Related to cp and cv

Derivative involves s, h, a or g
being held constant

Triple product rule

followed by
expansion rule

Derivative involves u, h, a or g
as the function, F

Expansion rule

Derivative involves T, s, P or v
only

Maxwells relation

Example 6:

Evaluate

(s / v) a in terms of cp, cv, T, P and v.

Eq. 5b

Cont. Example 5:

Example 7: Volumetric dependence

of cv for ideal gas

Determine how cv depends on volume by deriving an

expression for cv / v T . Evaluate the expression for an
ideal gas.

Cont. Example 6:

Example 8:
(a)

Derive a general formula to relate cp and cv.