Lecture Notes in Advanced Thermodynamics

Part 1.
V an Peter and Antali M ate
February 13, 2013
Contents
1 Introduction 2
1.1 Subject of thermodynamics . . . . . . . . . . . . . . . . . . . 2
1.2 Mathematical models in thermodynamics . . . . . . . . . . . . 2
1.2.1 Basic concepts . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.2 Classication of models . . . . . . . . . . . . . . . . . . 2
2 Thermostatics of discrete bodies 3
2.1 Simple compressible body . . . . . . . . . . . . . . . . . . . . 3
2.1.1 Basic notations . . . . . . . . . . . . . . . . . . . . . . 4
2.1.2 Denition of the model . . . . . . . . . . . . . . . . . . 4
2.1.3 Important relations from the model . . . . . . . . . . . 6
2.2 New variable sets and functions . . . . . . . . . . . . . . . . . 8
2.2.1 Change of variables . . . . . . . . . . . . . . . . . . . . 8
2.2.2 New quantities with Legendre transformation . . . . . 9
2.3 Densities, specic quantities . . . . . . . . . . . . . . . . . . . 12
2.3.1 Densities . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3.2 Specic quantities . . . . . . . . . . . . . . . . . . . . . 13
2.4 Simple model with specic quantities . . . . . . . . . . . . . . 15
2.4.1 Reformulating the model with specic quantities . . . . 15
2.4.2 Examining the constitutive equations . . . . . . . . . . 16
2.4.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . 18
1
1 Introduction
1.1 Subject of thermodynamics
What is the subject of thermodynamics?
elementary approach: physics of heat, temperature and energy
engineering advantage: performing practical calculations of energy
transfer processes (classical thermodynamics course)
advanced level: general background and framework of macroscopic
physics
engineering advantage: better understanding of other macroscopic
physics courses (solid mechanics, uid mechanics, classical thermody-
namics, electrodynamics, physical chemistry)
1.2 Mathematical models in thermodynamics
1.2.1 Basic concepts
thermodynamic system : a mathematical abstraction which is used for
modelling a piece of reality, a system is a collection of interacting bodies
thermodynamic body : the smallest individual piece of a system
state : the set of all pieces of information which determines our whole
knowledge from the system, time and space dependent.
state variables : mathematical objects which are used to represent the
state, they can be numbers, functions, etc. . .
1.2.2 Classication of models
dierent areas of thermodynamics dierent features of state variables
phenomenology - statistics
phenomenological: state variables are related directly to macroscopic
features of the material
statistical: state variables are related to the behaviour of the micro-
scopic particles, and macroscopic features are derived from them by
statistical methods (not covered in this subject)
2
thermostatics - thermodynamics
thermostatics: state variables do not depend on time
(analogy: mechanical statics)
thermodynamics: state variables can change in time
(analogy: mechanical dynamics)
discrete thermodynamics - continuum thermodynamics
discrete thermodynamics: state variables are homogeneous
(analogy: mechanics of point masses and rigid bodies)
continuum thermodynamics: state variables are space dependent
(analogy: continuum mechanics)
2 Thermostatics of discrete bodies
other names:
thermostatics of homogeneous bodies
equilibrium ,,thermodynamics
we can imagine a homogeneous body as a very small amount of material
or a box of material where all the properties are constant in space and time
2.1 Simple compressible body
simple compressible body: a thermodynamic body, which can be char-
acterized in equilibrium state by the mass (M), the volume (V ) and the
internal energy (E)
remarks:
in the following ,,body means this simple compressible body
this is an appropriate model for thermal and mechanical behaviour of
single-component gases
for other material types (solids, uids, multi-component gases, radia-
tion, etc.) or other physical properties (chemical, electrical, etc.) dif-
ferent, usually more complicated models are used
3
2.1.1 Basic notations
basic state variables: (E, V, M) (R
+
)
3
(they can be chosen intuitively or considering physical meaning)
state function: an f(E, V, M) : (R
+
)
3
R function which creates a new
state variable from the basic state variables
extensive scaling of a state function (f)(E, V, M) := f(E, V, M),
where is an arbitrary real number
(resizes the system, giving the value of the state function for a times
,,larger body )
intensive state function: f = f for R
(the state function remains constant if the body is resized)
extensive state function: f = f for R
(the state function is increasing linearly with the resizing)
remarks:
the function itself and the value of the function are not strictly distin-
guished in notation
in the denitions and following calculations equal sign (=) between
state functions means equality for all possible (E, V, M) values
E, V and M can be considered also as extensive state functions, e.g.
E(E, V, M) = E
the partial derivation of a function can be denoted in shorter way:
f(E, V, M)
E
=:
f
E

V,M
=:
E
f
2.1.2 Denition of the model
Denition(discrete thermostatic body):
a set of
_
_
_
T(E, V, M)
p(E, V, M)
(E, V, M)
_
_
_
state functions over the (E, V, M) state space
4
for that there exists a S(E, V, M) state function called entropy, which
has to full the following properties:
(P
1
) (entropy is a potential)
S
E

V,M
=
1
T
;
S
V

E,M
=
p
T
;
S
M

E,V
=

T
(1)
(P
2
) (entropy is increasing with energy)
S
E

V,M
> 0 (2)
(P
3
) (entropy is extensive)
S = S (3)
Consequence: The entropy is extensive if and only if there is a specic
entropy function: s(E/M, V/M) =
S(E,V,M)
M
(P
4
) (specic entropy is concave)
D
2
s(e, v) is a negative denite matrix (4)
Remarks:
T denotes the temperature, p is for the pressure and is called chemical
potential
T, p and functions are called state functions, they correspond to the
thermostatic system, the properties restrict the set of possible consti-
tutive functions due to physical principles
the properties are related, but cannot be derived from the laws of ther-
modynamics, the dynamical laws have an eect on the structure of the
system even in equilibrium state
5
Example: ideal gas
the well-known equations of the ideal gas (R is the gas constant and c
is the isochoric specic heat, they are real constants):
E = cMT; pV = MRT
from that the state functions are:
T(E, V, M) =
E
cM
p(E, V, M) =
MRT
V
=
RE
cV
let us choose the chemical potential function as:
(E, V, M) = c ln
E
M
+ Rln
V
M
for these functions an appropriate entropy function:
S(E, V, M) = Mc ln
E
M
+ MRln
V
M
+ M(c + R)
it can be easily checked that for c > 0 this entropy function fulls
properties (P
1
), (P
2
) and (P
3
), for proving the validity of (P
4
) a longer
calculation is required
2.1.3 Important relations from the model
Gibbs relation
the total dierential of the entropy function (d can be imagined as a
very small change in the quantity)
dS =
S
E

V,M
dE +
S
V

E,M
dV +
S
M

E,V
dM
using the (P
1
) property:
dS =
1
T
dE +
p
T
dV

T
dM (5)
after rearranging the Gibbs relation is obtained:
dE = TdS pdV + dM (6)
6
intensive property of T,p and :
let us calculate the resizing of (5):
dS =
1
T
dE +
p
T
dV

T
dM
E,V ,M are extensive (trivial) and S is extensive too due to property
(P
3
):
dS =
1
T
dE +
p
T
dV

T
dM
from that:
S
E

V,M
=
1
T
;
S
V

E,M
=
p
T
;
S
M

E,V
=

T
comparing them with property (P
1
):
T = T; p = p; = (7)
thus T, p and are intensive state functions
Potential relation
dierentiating property (P
1
) respect to :
_
S
E

V,M

_
E +
_
S
V

E,M

_
V +
_
S
M

E,V

_
M = S
using property (P
1
):
1
T
E +
p
T
V

T
M = S
using (7):
1
T
E +
p
T
V

T
M = S
after rearranging we get the potential relation:
E = TS pV + M (8)
7
2.2 New variable sets and functions
2.2.1 Change of variables
introduction of a new variable
given a function f(x, y)
the variable x is changed to z with the substitution x = x(z, y)
the new function is

f(y, z) := f
_
x(y, z), z
_
(9)
derivatives respect to the new variable
(partial) dierentiating (9) respect to z

z

f|
y
=
x
f|
y

z
x|
y
rearranging:

x
f|
y
=

z

f|
y

z
x|
y
(10)
special case z = f

x
f|
y
=
1

f
x|
y
derivatives respect to the remaining variable
(partial) dierentiating (9) respect to y:

y

f|
z
=
x
f|
y

y
x|
z
+
y
f|
x
using (10):

y

f|
z
=

z

f|
y

z
x|
y

y
x|
z
+
y
f|
x
rearranging:

y
f|
x
=
y

f|
z


y
x|
z

z
x|
y

z

f|
y
(11)
special case z = f

y
f|
x
=
y
x|
f

x
f|
y
8
Example: internal energy
let us change the variable space from the standard (E, V, M) to (S, V, M)
the Gibbs relation remains valid if we change the T(E, V, M) function
to T(S, V, M) and so on, so the internal energy is a potential of the
(T, p, ) functions:
E
S

V,M
= T;
E
V

S,M
= p;
E
M

S,V
= (12)
in the previous notations x = E, z = S and the ,,y-s are V and M
let f be p(E, V, M), therefore (10) becomes:

E
p|
V,M
=

S
p|
V,M

S
E|
V,M
using (12):

E
p|
V,M
=

S
p|
V,M
T
now applying (11):

V
p|
E,M
=
V
p|
S,M


V
E|
S,M

S
E|
V,M

S
p|
V,M
using (12):

V
p|
E,M
=
V
p|
S,M
+
p
T

S
p|
V,M
2.2.2 New quantities with Legendre transformation
introduction of the Legendre transform
given a function f(x, y)
the variable x is changed to z with the substitution x = x(z, y)
the Legendre transform of f(x, y) is g(z, y) which is determined by the
following two properties:
g(z, y) + x(z, y) z = f
_
x(z, y), y
_
(13)

z
g|
y
= x(z, y) (14)
9
derivatives respect to the new variable
(partial) dierentiating (13) respect to z

z
g|
y
+ x(z, y) + z
z
x|
y
=
x
f|
y

z
x|
y
using (14):
z =
x
f|
y
(15)
so z can be also considered as a z(x, y) function
from (14) and (15) comes that the derivatives of f and g are inverse
functions
x and z are called conjugated variables
derivatives respect to the variable, that is no transformed
(partial) dierentiating (13) respect to y:

y
g|
z
+
y
x|
z
z =
x
f|
y

y
x|
z
+
y
f|
x
using (15):

y
g|
z
=
y
f|
x
(16)
the exact equality is valid if the x(z, y) substitution is done on the right
side after the derivation
thus the Legendre transformation keeps constant the derivatives respect
to the remaining variables
example: free energy
let us start with the f = E(S, V, M) function and x = E, then accord-
ing to (15):
z =
S
E|
V,M
due to (12):
z = T
let the new function be F(T, V, M) and called Helmholtz free energy,
then the formula of the Legendre transformation in (13) becomes:
F + ST = E
so the denition of the free energy is:
F = E TS (17)
10
substituting to the potential relation (8) :
F = pV + M
(potential relation for free energy)
dierentiating (17)
dF = dE d(TS) = dE SdT TdS
using the Gibbs-relation (6):
dF = TdS pdV + dM SdT TdS
dF = SdT pdV + dM
(Gibbs relation for free energy)
thus after the S T interchange the free energy is an F(T, V, M) func-
tion, which is a potential of the S(T, V, M), p(T, V, M) and (T, V, M)
functions:
F
T

V,M
= S;
F
V

T,M
= p;
F
M

T,V
=
(we can check the validity of (16))
it can be checked easily that F is not an extensive function over its
(T, V, M) variable space, but it is extensive if we transform the variables
to the standard (E, V, M) variables
the whole procedure can be applied similarly to get the enthalpy (H)
and the Gibbs free energy (G), the results can be found in the tables,
E, F, H and G are called thermodynamic potentials
quantity denition potential relation
energy - E = TS pV + M
Helmholtz free energy F := E TS F = pV + M
enthalpy H := E + pV H = ST + M
Gibbs free energy G := E TS + pV G = M
Table 1: Important thermodynamic potentials - denitions
11
quantity variables Gibbs relation
energy E(S, V, M) dE = TdS pdV + dM
Helmholtz free energy F(T, V, M) dF = SdT pdV + dM
enthalpy H(S, p, M) dH = TdS + V dp + dM
Gibbs free energy G(T, p, M) dG = SdT + V dp + dM
Table 2: Important thermodynamic potentials - variables
2.3 Densities, specic quantities
the extensive and intensive properties are constraints
one of the extensive variables can be eliminated
it can be useful to choose a reference variable
usually the volume (densities) and the mass (specic quantities) are
used for reference
2.3.1 Densities
transformation of the basic state variables
energy density:
:=
E
V
mass density:
:=
M
V
transformation of the state functions
the (E, V, M) state space can be simplied to (, )
considering an extensive state function:

f(, ) := f (, 1, ) = f
_
E
V
, 1,
M
V
_
=
V f
_
E
V
, 1,
M
V
_
V
=
f(E, V, M)
V
specially:

E = ;

M =
12
considering an intensive state function:
g(, ) := g (, 1, ) = g
_
E
V
, 1,
M
V
_
= g(E, V, M)
the functions over the new state space (, ) are intensive functions
potential relation for densities:
let us divide (8) by V :
E
V
= T
S
V
p +
M
V
using the denition of the densities:
= Ts p + (18)
Gibbs relation for densities:
let us substitute the densities to (6):
d(V ) = Td(sV ) pdV + d(V )
using the derivation rule d(xy) = xdy + ydx:
V d + dV = TV ds + TsdV pdV + V d + dV
dV ( Ts + p ) + V (d Tds d) = 0
the expression in the rst bracket is zero due to (18), therefore the
Gibbs relation for densities:
d = Tds + d (19)
2.3.2 Specic quantities
transformation of the basic state variables
specic energy:
e :=
E
M
specic volume:
v :=
V
M
13
transformation of the state functions
the (E, V, M) state space is simplied to (e, v)
considering an extensive state function:

f(e, v) := f (e, v, 1) = f
_
E
M
,
V
M
, 1
_
=
Mf
_
E
M
,
V
M
, 1
_
M
=
f(E, V, M)
M
specially:

E = e;

V = v
considering an intensive state function:
g(e, v) := g (e, v, 1) = g
_
E
M
,
V
M
, 1
_
= g(E, V, M)
the functions over the state space (e, v) are neither extensive not inten-
sives
potential relation for specic quantities:
let us divide (8) by M:
E
M
= T
S
M
p
V
M
+
using the denitions:
e = Ts pv + (20)
Gibbs relation for specic quantities:
let us substitute the specic quantities to (6):
d(eM) = Td(sM) pd(vM) + dM
using the derivation rule:
Mde + edM = Tvds + TsdM pvdM pMdv + dM
dM( Ts + pv ) + M(de Tds + pdv) = 0
from (20) the rst bracket equals zero, thus the Gibbs relation:
de = Tds pdv (21)
14
extensive quantity (A) V M E S F G H
density (A/V ) 1 s
specic quantity (A/M) v 1 e s f g h
Table 3: Densities and specic quantities
2.4 Simple model with specic quantities
2.4.1 Reformulating the model with specic quantities
Denition(discrete thermostatic body for specic quantities):
a set of
_
T(e, v)
p(e, v)
_
state functions over the (e, v) state space
for that there exists a s(e, v) state function called specic entropy, which
has to full the following properties:
(B
1
) (specic entropy is a potential)
s
e

v
=
1
T
;
s
v

e
=
p
T
(22)
(B
2
) (specic entropy is increasing with energy)
s
e

v
> 0 (23)
(B
3
) (specic entropy is concave)
D
2
s(e, v) is a negative denite matrix (24)
remarks:
if the mass M is constant, this and the previous models are equivalent
the property corresponding to (P
3
) is missing, this property was used
to reduce the three variables to two
we do not require the complicated extensive and intensive properties
15
2.4.2 Examining the constitutive equations
motivation
T(e, v) and p(e, v) functions are often given as empirical approximations
it is useful to check if they full the propertys of thermostatics
sometimes the propertys can be used to make restrictions to the pa-
rameters of the model
Condition of the potential property of entropy
if the entropy function is twice dierentiable then the mixed second
partial derivatives must be equal

2
s(e, v)
ve
=

2
s(e, v)
ev
using property (B
1
):

e
_
1
T(e, v)
_
=

e

v
_
p(e, v)
T(e, v)
_
(25)
this condition is useful to check the T and p functions against the (B
1
)
property, without calculating the entropy function
if (25) is not valid, then there exists no s(e, v) function, if the condition
fulls, then s exists and the gas described by T and p functions is called
entropic
Condition of the increasing property of entropy
property (B
2
) is simple, it requires only
s
e

v
> 0
if the property (B
1
) is substituted, a very simple condition is obtained:
T(e, v) > 0 (26)
therefore the range of the temperature function must be positive
16
Condition of the concave property of specic entropy
the condition of property (B
2
) is called thermodynamic stability, which
requires the concavity of the specic entropy function
the concavity requires that the Hesse-matrix of the specic entropy
function, this D
2
s(e, v) has to be negative denite (or D
2
s(e, v) posi-
tive denite) whenever the function is two times continuously dieren-
tiable
the positive deniteness of a symmetric matrix can be investigated by
the Sylvester criteria, a matrix
_
a
11
a
12
a
12
a
22
_
is positive denite if and only if a
11
> 0 and a
11
a
22
a
2
12
> 0
applying to the entropy function:
Ds =
_

e
s|
v

v
s|
e

=
_
1
T
p
T

D
2
s =
_
_

e
_
1
T
_

v

v
_
1
T
_

e
_
p
T
_

v

v
_
p
T
_

e
_
_
=
=
_
_
1
T
2

e
T|
v
1
T
2

v
T|
e

1
T

e
p|
v
+
p
T
2

e
T|
v

1
T

v
p|
e
+
p
T
2

v
T|
e
_
_
using the a
11
> 0 condition:
1
T
2

e
T|
v
> 0

e
T|
v
> 0 (27)
using the a
11
a
22
a
2
12
> 0 condition:
1
T
4
_

e
T|
v
(p
v
T|
e
T
v
p|
e
)
v
T|
e
(p
e
T|
v
T
e
p|
v
)
_
> 0
1
T
3
_

v
T|
e

e
p|
v

v
p|
e

e
T|
v
_
> 0

e
T|
v
T
3
_

v
p|
e


v
T|
e

e
T|
v

e
p|
v
_
> 0
17
the bracket equals to
v
p|
T
because of (11), therefore:

e
T|
v
T
3

v
p|
T
> 0

e
T|
v
is positive due to (27) and T
3
is positive due to (26), thus

v
p|
T
< 0 (28)
(27) and (28) are a particular example of the le Chatelier-Brown prin-
ciple.
2.4.3 Examples
ideal gas
the thermic equation of state:
pv = RT
the caloric equation of state:
e = cT
from that the standard state functions:
T(e, v) =
e
c
p(e, v) =
Re
cv
the condition of (25):

e
_
1
T(e, v)
_
= 0

v
_
p(e, v)
T(e, v)
_
= 0
they are equal, hence the ideal gas model is entropic
the condition (26): because the energy (e) is positive by denition, the
condition for the positive temperature is:
c > 0
18
the condition (27):

e
T|
v
=
1
c
> 0
c > 0
the condition (28):
p(T, v) =
RT
v

v
p|
T
=
RT
v
2
from (26) we get:
R > 0
therefore if c > 0 and R > 0 then an ideal gas fulls the properties of
thermostatics
van der Waals gas
the termic equation of state is:
p =
RT
v b

a
v
2
the caloric equation of state is:
T =
e
c
+
a
cv
therefore the standard state functions:
T(e, v) =
e
c
+
a
cv
p(e, v) =
Re
c(v b)
+
Ra
cv(v b)

a
v
2
the condition (25):
1
T
=
c
e +
a
v
p
T
=
R
v b

a
v
2

c
e +
a
v
it can be checked that

e
_
1
T(e, v)
_
=

e

v
_
p(e, v)
T(e, v)
_
=
ac
(ev + a)
2
therefore the van der Waals gas model is entropic
19
the condition (26):
e
c
+
a
cv
> 0
if c > 0 then ev > a, if c < 0 then ev < a
the condition (27):

e
T|
v
=
1
c
> 0
c > 0
the condition (28):

v
p|
T
=
RT
(v b)
2
+
2a
v
3
< 0
Therefore the van der Waals gas body fulls (B
2
) and (B
3
) properties
for a given domain of (e, v) restricted by the parameters.
20