Lecture Notes in Advanced Thermodynamics

Part 1.

Van Peter and Antali Mate

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 Classification of models . . . . . . . . . . . . . . . . . . 2

2 Thermostatics of discrete bodies 3

2.1 Simple compressible body . . . . . . . . . . . . . . . . . . . . 3
2.1.1 Basic notations . . . . . . . . . . . . . . . . . . . . . . 4
2.1.2 Definition 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, specific quantities . . . . . . . . . . . . . . . . . . . 12
2.3.1 Densities . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3.2 Specific quantities . . . . . . . . . . . . . . . . . . . . . 13
2.4 Simple model with specific quantities . . . . . . . . . . . . . . 15
2.4.1 Reformulating the model with specific 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, fluid 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 Classification of models

different areas of thermodynamics different 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, fluids, 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 definitions 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 ) f 
=: =: E f
E E  V,M

2.1.2 Definition of the model

Definition(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 fulfil the following properties:

(P1 ) (entropy is a potential)

  
S  1 S  p S 
= ; = ; = (1)
E V,M
 T V E,M
 T M E,V
 T

(P2 ) (entropy is increasing with energy)


S 
>0 (2)
E V,M

(P3 ) (entropy is extensive)

S=S (3)

Consequence: The entropy is extensive if and only if there is a specific

entropy function: s(E/M, V /M ) = S(E,V,M
M
)

(P4 ) (specific entropy is concave)

D2 s(e, v) is a negative definite 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 effect 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 specific heat, they are real constants):

E = cM T ; pV = M RT

from that the state functions are:

E
T (E, V, M ) =
cM
M RT RE
p(E, V, M ) = =
V cV
let us choose the chemical potential function as:
E V
(E, V, M ) = c ln + R ln
M M
for these functions an appropriate entropy function:
E V
S(E, V, M ) = M c ln + M R ln + M (c + R)
M M
it can be easily checked that for c > 0 this entropy function fulfils
properties (P1 ), (P2 ) and (P3 ), for proving the validity of (P4 ) a longer
calculation is required

2.1.3 Important relations from the model

Gibbs relation
the total differential of the entropy function (d can be imagined as a
very small change in the quantity)
  
S  S  S 
dS = dE + dV + dM
E V,M V E,M M E,V

using the (P1 ) property:

1 p
dS = dE + dV dM (5)
T T T
after rearranging the Gibbs relation is obtained:

dE = T dS pdV + dM (6)

6
intensive property of T ,p and :

let us calculate the resizing of (5):

1 p
dS = dE + dV dM
T T T

E,V ,M are extensive (trivial) and S is extensive too due to property

(P3 ):
1 p
dS = dE + dV dM
T T T
from that:
  
S  1 S  p S 
= ; = ; =
E V,M
 T V E,M
 T M E,V
 T

comparing them with property (P1 ):

T = T; p = p; = (7)

thus T , p and are intensive state functions

Potential relation

differentiating property (P1 ) respect to :

 !  !  !
S  S  S 
E+ V + M =S
E V,M V E,M M E,V

using property (P1 ):

1 p
E+ V M =S
T T T

using (7):
1 p
E+ V M =S
T T T
after rearranging we get the potential relation:

E = T S 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) differentiating (9) respect to z

z f|y = x f |y z x|y

rearranging:
z f|y
x f |y = (10)
z x|y

special case z = f
1
x f |y =
f x|y

derivatives respect to the remaining variable

(partial) differentiating (9) respect to y:

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

using (10):
z f|y
y f|z = y x|z + y f |x
z x|y
rearranging:
y x|z
y f |x = y f|z z f|y (11)
z x|y

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  E  E 
= T; = p; = (12)
S V,M V S,M M S,V

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:

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

using (12):
S p|V,M
E p|V,M =
T
now applying (11):

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

using (12):
p
V p|E,M = V p|S,M + S p|V,M
T

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) differentiating (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) differentiating (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 definition of the free energy is:
F = E TS (17)

10
 substituting to the potential relation (8) :

F = pV + M

(potential relation for free energy)

differentiating (17)

dF = dE d(T S) = dE SdT T dS

using the Gibbs-relation (6):

dF = T dS pdV + dM SdT T dS

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  F  F 
= S; = p; =
T V,M V T,M 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 definition potential relation

energy - E = T S pV + M
Helmholtz free energy F := E T S F = pV + M
enthalpy H := E + pV H = ST + M
Gibbs free energy G := E T S + pV G = M

Table 1: Important thermodynamic potentials - definitions

11
 quantity variables Gibbs relation
energy E(S, V, M ) dE = T dS pdV + dM
Helmholtz free energy F (T, V, M ) dF = SdT pdV + dM
enthalpy H(S, p, M ) dH = T dS + V dp + dM
Gibbs free energy G(T, p, M ) dG = SdT + V dp + dM

Table 2: Important thermodynamic potentials - variables

2.3 Densities, specific 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 (specific 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 simplified to (, )

considering an extensive state function:

E
, 1, M
 

E M Vf f (E, V, M )
f(, ) := f (, 1, ) = f , 1, = V V
=
V V V V

specially:
E = ; M =

12
 considering an intensive state function:
 
E M
g(, ) := g (, 1, ) = g , 1, = g(E, V, M )
V V

the functions over the new state space (, ) are intensive functions

potential relation for densities:

let us divide (8) by V :
E S M
=T p+
V V V

using the definition of the densities:

= T s p + (18)

Gibbs relation for densities:

let us substitute the densities to (6):

d(V ) = T d(sV ) pdV + d(V )

using the derivation rule d(xy) = xdy + ydx:

V d + dV = T V ds + T sdV pdV + V d + dV

dV ( T s + p ) + V (d T ds d) = 0

the expression in the first bracket is zero due to (18), therefore the
Gibbs relation for densities:

d = T ds + d (19)

2.3.2 Specific quantities

transformation of the basic state variables
specific energy:
E
e :=
M
specific volume:
V
v :=
M

13
transformation of the state functions
the (E, V, M ) state space is simplified to (e, v)
considering an extensive state function:
E V
 

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

considering an intensive state function:

 
E V
g(e, v) := g (e, v, 1) = g , , 1 = g(E, V, M )
M M

the functions over the state space (e, v) are neither extensive not inten-
sives

potential relation for specific quantities:

let us divide (8) by M :
E S V
=T p +
M M M
using the definitions:
e = T s pv + (20)

Gibbs relation for specific quantities:

let us substitute the specific quantities to (6):
d(eM ) = T d(sM ) pd(vM ) + dM

using the derivation rule:

M de + edM = T vds + T sdM pvdM pM dv + dM
dM ( T s + pv ) + M (de T ds + pdv) = 0

from (20) the first bracket equals zero, thus the Gibbs relation:

de = T ds pdv (21)

14
 extensive quantity (A) V M E S F G H
density (A/V ) 1 s
specific quantity (A/M ) v 1 e s f g h

Table 3: Densities and specific quantities

2.4 Simple model with specific quantities

2.4.1 Reformulating the model with specific quantities
Definition(discrete thermostatic body for specific 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 specific entropy, which
has to fulfil the following properties:

(B1 ) (specific entropy is a potential)

 
s  1 s  p
= ; = (22)
e v T
 v e T


(B2 ) (specific entropy is increasing with energy)


s 
>0 (23)
e v

(B3 ) (specific entropy is concave)

D2 s(e, v) is a negative definite matrix (24)

remarks:
if the mass M is constant, this and the previous models are equivalent
the property corresponding to (P3 ) 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 fulfil 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 differentiable then the mixed second

partial derivatives must be equal

2 s(e, v) 2 s(e, v)
=
ve ev

using property (B1 ):

     
 1  p(e, v)
= (25)
v e T (e, v) e v T (e, v)

this condition is useful to check the T and p functions against the (B1 )
property, without calculating the entropy function

if (25) is not valid, then there exists no s(e, v) function, if the condition
fulfils, then s exists and the gas described by T and p functions is called
entropic

Condition of the increasing property of entropy

property (B2 ) is simple, it requires only


s 
>0
e v

if the property (B1 ) 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 specific entropy
the condition of property (B2 ) is called thermodynamic stability, which
requires the concavity of the specific entropy function
the concavity requires that the Hesse-matrix of the specific entropy
function, this D2 s(e, v) has to be negative definite (or D2 s(e, v) posi-
tive definite) whenever the function is two times continuously differen-
tiable
the positive definiteness of a symmetric matrix can be investigated by
the Sylvester criteria, a matrix
 
a11 a12
a12 a22

is positive definite if and only if a11 > 0 and a11 a22 a212 > 0
applying to the entropy function:

Ds = e s|v v s|e = T1 Tp
   



e T1 v v T1 e
D2 s =
 =
e p  v p 


T v T e

1 1
T |v
T2 e
T |e
T2 v
=
T e p|v + Tp2 e T |v T1 v p|e + Tp2 v T |e
1

using the a11 > 0 condition:

1
e T |v > 0
T2
e T |v > 0 (27)

using the a11 a22 a212 > 0 condition:

1

e T |v (p v T |e T v p|e ) v T |e (p e T |v T e p|v ) >0
T4
1

3
v T |e e p|v v p|e e T |v > 0
T
 
e T |v v T |e
3 v p|e e p|v > 0
T e T |v

17
 the bracket equals to v p|T because of (11), therefore:
e T |v
v p|T > 0
T3

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:

e
T (e, v) =
c
Re
p(e, v) =
cv
the condition of (25):
  
 1
=0
v e T (e, v)
  
 p(e, v)
=0
e v T (e, v)
they are equal, hence the ideal gas model is entropic

the condition (26): because the energy (e) is positive by definition, the
condition for the positive temperature is:

c>0

18
 the condition (27):
1
e T |v = >0
c
c>0
the condition (28):
RT
p(T, v) =
v
RT
v p|T = 2
v
from (26) we get:
R>0
therefore if c > 0 and R > 0 then an ideal gas fulfils the properties of
thermostatics

van der Waals gas

the termic equation of state is:
RT a
p= 2
vb v

the caloric equation of state is:

e a
T = +
c cv

therefore the standard state functions:

e a
T (e, v) = +
c cv
Re Ra a
p(e, v) = + 2
c(v b) cv(v b) v
the condition (25):
1 c
=
T e + av
p R a c
= 2 a
T vb v e+ v
it can be checked that
     
 1  p(e, v) ac
= =
v e T (e, v)
 e v T (e, v)
 (ev + a)2
therefore the van der Waals gas model is entropic

19
 the condition (26):
e a
+ >0
c cv
if c > 0 then ev > a, if c < 0 then ev < a

the condition (27):

1
e T |v = >0
c
c>0

the condition (28):

RT 2a
v p|T = + <0
(v b)2 v 3

Therefore the van der Waals gas body fulfils (B2 ) and (B3 ) properties
for a given domain of (e, v) restricted by the parameters.

20