Lecture Notes in Advanced Thermodynamics

Part 1.

Ván Péter and Antali Máté

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 ◦λ)(E, V, M ) := f (λE, λV, λM ),

where λ is an arbitrary real number
(resizes the system, giving the value of the state function for a λ times
,,larger” body )

intensive state function: f ◦ λ = f for ∀λ ∈ R

(the state function remains constant if the body is resized)

extensive state function: f ◦ λ = λ · f for ∀λ ∈ 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 )
µ(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  µ
= ; = ; =− (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◦λ=λ·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 µ is called chemical

potential

– T, p and µ 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
µ(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 µ
dS = dE + dV − dM (5)
T T T
– after rearranging the Gibbs relation is obtained:

dE = T dS − pdV + µdM (6)

6
intensive property of T ,p and µ:

– let us calculate the resizing of (5):

1 p◦λ µ◦λ
dS ◦ λ = dE ◦ λ + dV ◦ λ − dM ◦ λ
T ◦λ T ◦λ T ◦λ

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

(P3 ):
1 p◦λ µ◦λ
λdS = λdE + λdV − λdM
T ◦λ T ◦λ T ◦λ
– from that:
  
∂S  1 ∂S  p◦λ ∂S  µ◦λ
= ; = ; =−
∂E V,M
 T ◦λ ∂V E,M
 T ◦λ ∂M E,V
 T ◦λ

– comparing them with property (P1 ):

T ◦ λ = T; p ◦ λ = p; µ◦λ=µ (7)

– thus T , p and µ are intensive state functions

Potential relation

– differentiating property (P1 ) respect to λ:

 !  !  !
∂S  ∂S  ∂S 
◦λ E+ ◦λ V + ◦λ M =S
∂E V,M ∂V E,M ∂M E,V

– using property (P1 ):

1 p◦λ µ◦λ
E+ V − M =S
T ◦λ T ◦λ T ◦λ

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

E = T S − pV + µM (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

fˆ(y, z) := f x(y, z), z


(9)

derivatives respect to the new variable

– (partial) differentiating (9) respect to z

∂z fˆ|y = ∂x f |y · ∂z x|y

– rearranging:
∂z fˆ|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 fˆ|z = ∂x f |y · ∂y x|z + ∂y f |x

– using (10):
∂z fˆ|y
∂y fˆ|z = · ∂y x|z + ∂y f |x
∂z x|y
– rearranging:
∂y x|z
∂y f |x = ∂y fˆ|z − · ∂z fˆ|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, µ) functions:
  
∂E  ∂E  ∂E 
= T; = −p; =µ (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 + µM

(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 + µdM − SdT − T dS

dF = −SdT − pdV + µdM

(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 µ(T, V, M )
functions:
  
∂F  ∂F  ∂F 
= −S; = −p; =µ
∂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 + µM
Helmholtz free energy F := E − T S F = −pV + µM
enthalpy H := E + pV H = ST + µM
Gibbs free energy G := E − T S + pV G = µM

Table 1: Important thermodynamic potentials - definitions

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

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
ε :=
V
– mass density:
M
ρ :=
V

transformation of the state functions

– the (E, V, M ) state space can be simplified to (ε, ρ)

– considering an extensive state function:

E
, 1, M
 

E M Vf f (E, V, M )
fˆ(ε, ρ) := f (ε, 1, ρ) = f , 1, = V V
=
V V V V

specially:
Ê = ε; M̂ = ρ

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

– the functions over the new state space (ε, ρ) are intensive functions

potential relation for densities:

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

– using the definition of the densities:

ε = T s − p + µρ (18)

Gibbs relation for densities:

– let us substitute the densities to (6):

d(εV ) = T d(sV ) − pdV + µd(ρV )

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

V dε + εdV = T V ds + T sdV − pdV + µV dρ + µρdV

dV (ε − T s + p − µρ) + V (dε − T ds − µdρ) = 0

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

dε = T ds + µdρ (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:
Ẽ = e; Ṽ = v

– considering an intensive state function:

 
E V
g̃(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 +µ
M M M
– using the definitions:
e = T s − pv + µ (20)

Gibbs relation for specific quantities:

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

– using the derivation rule:

M de + edM = T vds + T sdM − pvdM − pM dv + µdM
dM (ε − T s + pv − µ) + 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 ρ ε 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)
=
∂v∂e ∂e∂v

– 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
v−b 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 v−b 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