Balance Equations and Entropy Inequality

J. BLUHM
Institut für Mechanik
Fakultät für Ingenieurwissenschaften, Abteilung Bauwissenschaften
Universität Duisburg-Essen, 45117 Essen

Literature:
de Boer, Reint: Vektor- und Tensorrechnung für Ingenieure, Springer-
Verlag, Berlin · Heidelberg · New York, 1982.
Hutter, Kolumban & Jöhnk, Klaus: Continuum methods of physical
modeling, Springer-Verlag, Berlin · Heidelberg · New York, 2004.
Holzapfel, Gerhard A.: Nonlinear solid mechanics – A continuum ap-
proach for engineering. John Wiley & Sons, 2000.
Müller, Ingo: Grundzüge der Thermodynamik, Springer-Verlag, Berlin ·
Heidelberg · New York, 2001.
1. Balance equations and entropy inequality

The balance equations as well as the entropy inequality are material indepen-
dent realtions:

• Balance of mass – mass conservation, continuity equation;

• Balance of momentum – conservation of momentum,
principle of linear momentum,
Newton‘s equation of motion;
• Balance of moment of momentum – conservation of angular momentum;
• Balance of energy – first law of thermodynamics;
• Entropy inequality – second law of thermodynamics,
Clausius-Duhem inequality.
The structure of the balance laws of mass, momentum, angular momentum
and energy for a single body is given by

( B )· = ( E ) ,

where the symbol ( . . . )· denotes the material time derivative of the corre-
sponding quantity following the motion of the single body.

1
structure of the ( B )· = (E )
balance equations
for a single body

B E

balance of mass mass 0

(M)

balance of momentum external forces

momentum
(l) (k)

balance of angular external moments

angular momentum momentum
( h(0) ) ( m(0) )

balance of energy internal and increments of the

kinetic energy mechanical and
non-mechanical
work
(E + K) (W + Q)

Table 1.1: Structure of the balance laws for a single body

2
1.1 Balance of mass

The axiom of the balance of mass (conservation of mass) reads

Ṁ = 0 , (1.1)

where
Z
M = ρ dv (1.2)
B

denotes the mass at time t.

With the material time derivative

Z Z Z
Ṁ = ( ρ dv ) = ( ρ J dV ) =
· ·
( ρ J )· dV
B B0 B0
Z
= ( ρ̇ J + ρ J̇ ) dV
B0
Z
= ( ρ̇ J + ρ J div ẋ ) dV (1.3)
B0
Z
= ( ρ̇ + ρ div ẋ ) J dV
B0
Z
= ( ρ̇ + ρ div ẋ ) dv
B

one obtains the following form of the balance of mass:

Z
( ρ̇ + ρ div ẋ ) dv = 0 . (1.4)
B
Considering
∂ρ
ρ̇ ( x , t ) = + grad ρ · ẋ (1.5)
∂t
the alternative representation form

3
 Z
∂ρ
( + grad ρ · ẋ + ρ div ẋ ) dv = 0
∂t | {z }
B = div( ρ ẋ )
=⇒
Z
∂ρ
[ + div( ρ ẋ ) ] dv = 0 (1.6)
∂t
B
can be derived. With the divergence theorem
Z Z
div( ρ ẋ ) dv = ρ ẋ · n da (1.7)
B ∂B
Equation (1.6) can be transferred to the global statement
Z Z
∂ρ
dv = − ρ ẋ · n da . (1.8)
∂t
B ∂B

The relations (1.4) and (1.6) are denoted as the Lagrange and Euler form of
the balance of mass.

Provided that the integrand is continuous, from (1.4) and (1.6), respectively,
directly one concludes to the local statement of the balance of mass:

ρ̇ + ρ div ẋ = 0 (1.9)

and
∂ρ
+ div( ρ ẋ ) = 0 , (1.10)
∂t
respectively. With help of
1
div ẋ = J̇ (1.11)
J
Equation (1.9) can be reformulated:
1 1
ρ̇ = − J̇ . (1.12)
ρ J
The time integration of the aformentioned relation yields the integral form of
local statement of the Lagrange form of the balance of mass:

4
 Zt Zt
1 1
ρ̇ dt = − J̇ dt
ρ J
t0 t0

ln ρ |tt0 = − ln J |tt0

ln ρ (t) − ln ρ (t0 ) = − ln J (t) + ln J (t0 )

ln ρ − ln ρ0 = − ln J + 0

→
ρ 1
ln = ln
ρ0 J
=⇒
ρ0
J = det F = . (1.13)
ρ
The quantity ρ0 = const. denotes the density of the undeformed reference
placement at time t = t0 , i.e. F = I and det F = J = 1.

5
 Summary: Balance of mass

Z
Axiom ( ρ dv )· = 0
B

globale statements

reference Z
placement M = ρ0 dV = konst.
B0

actual Z
placement ( ρ̇ + ρ div ẋ ) dv = 0
B
Z Z
∂ρ
dv = − ρ ẋ · n da
∂t
B ∂B

local statements

reference
placement ρ0 = konst.

actual
placement ρ̇ + ρ div ẋ = 0

∂ρ
+ div( ρ ẋ ) = 0
∂t

integrale
ρ0
form J = det F =
ρ

6
1.2 Balance of momentum

The axiom of the balance of momentum reads:

l̇ = k . (1.14)
Therein,
Z
l = ρ ẋ dv ,
B
Z Z Z Z (1.15)
k = ρ b dv + t da = ρ b dv + σ n da
B ∂B B ∂B

denote the vector of momentum and the vector of external forces. The external
forces k are to be split into two parts, namely into a part which is caused by
the local external body force ρ b integrated over the actual volume and a part
caused by the external contact force t = σ n integrated over the surface of the
actual placement. The quantity σ is the Cauchy stress tensor.

With the material time derivative of the momentum

Z Z Z
l̇ = ( ρ ẋ dv ) = ( ρ ẋ J dV ) =
· ·
( ρ J ẋ )· dV
B B0 B0
Z
= ( ρ̇ J ẋ + ρ J̇ ẋ + ρ J ẍ ) dV
B0
Z
= [ ρ̇ J ẋ + ρ J ( div ẋ ) ẋ + ρ J ẍ ] dV
B0
Z
= [ ρ̇ ẋ + ρ ( div ẋ ) ẋ + ρ ẍ ] J dV (1.16)
B0
Z
= [ ρ̇ ẋ + ρ ( div ẋ ) ẋ + ρ ẍ ] dv
B
Z
= [ ( ρ̇ + ρ div ẋ ) ẋ + ρ ẍ ] dv
| {z }
B = 0
Z
= ρ ẍ dv
B

7
and the divergence theorem
Z Z
σ n da = div σ dv (1.17)
∂B B
the balance of momentum con be transferred to
Z Z
ρ ẍ dv = ( div σ + ρ b ) dv
B B
=⇒
Z
[ div σ + ρ ( b − ẍ ) ] dv = o . (1.18)
B
This is the so-called Lagrange form of the balance equation. Using
ρ ẍ = (ρ ẋ )· − ρ̇ ẋ
∂( ρ ẋ )
= + [ grad( ρ ẋ ) ] ẋ − ρ̇ ẋ
∂t
∂( ρ ẋ )
= + [ grad( ρ ẋ ) ] ẋ − ( − ρ div ẋ) ẋ
∂t (1.19)
∂( ρ ẋ )
= + [ grad( ρ ẋ ) ] ẋ + ρ ẋ div ẋ
∂t | {z }
= div( ρ ẋ ⊗ ẋ )
∂( ρ ẋ )
= + div( ρ ẋ ⊗ ẋ )
∂t
one obtains the alternative form
Z
∂( ρ ẋ )
{ div σ + ρ b − [ + div( ρ ẋ ⊗ ẋ ) ] } dv = o
∂t
B
→
Z
∂( ρ ẋ )
[ div σ + ρ b − − div( ρ ẋ ⊗ ẋ )] dv = o
∂t
B
→
Z
∂( ρ ẋ )
[ div( σ − ρ ẋ ⊗ ẋ ) + ρ b − ] dv = o
∂t
B
=⇒

8
 Z
∂( ρ ẋ )
[ − div( σ − ρ ẋ ⊗ ẋ ) − ρ b ] dv = o . (1.20)
∂t
B
Considering the divergence theorem
Z Z
div( σ − ρ ẋ ⊗ ẋ ) dv = ( σ − ρ ẋ ⊗ ẋ ) n da (1.21)
B ∂B
the Euler form of the balance of momentum can be gained:
Z Z
∂( ρ ẋ )
( − ρ b ) dv = ( σ − ρ ẋ ⊗ ẋ ) n da . (1.22)
∂t
B ∂B

Equation (1.18) and (1.20), respectively, directly yields the local stament

div σ + ρ ( b − ẍ ) = o (1.23)

and
∂( ρ ẋ )
− div( σ − ρ ẋ ⊗ ẋ ) − ρ b = o , (1.24)
∂t
respectively, of the balance of momentum.

With the relation

1 1
σ = F S FT = P FT (1.25)
J J
for the Cauchy stress tensor, where

S = J F−1 σ FT−1 = F−1 P , P = F S = J σ FT−1 (1.26)

are the 2. (symmetric) and 1. (non-symmetric) Piola-Kirchhoff stress tensor,

and the transport theorem

da = J FT−1 dA (1.27)

regarding surface elements, the volume integral of the divergence of σ can be

transferred to

9
 Z Z Z Z
div σ dv = σ n da = σ da = J σ FT−1 dA
B ∂B ∂B ∂B0
Z Z
= P dA = P n0 dA (1.28)
∂B0 ∂B0
Z
= Div P dV .
B0

Considering the transport theorem of volume elements and the integral form
of the balance of mass,

dv = J dV , ρ = J−1 ρ0 , (1.29)

the balance equation (1.18) can be reformulated as follows:

Z Z
ρ0 ẍ dV = ( Div P + ρ0 b ) dV .
B0 B

=⇒
Z
[ Div P + ρ0 ( b − ẍ ) ] dV = o . (1.30)
B0

Thus, with respect to the reference placement the local statement of the bal-
ance of momentum (Lagrange form) is given by

Div P + ρ0 ( b − ẍ ) = o . (1.31)

10
 Summary: Balance of momentum

Z Z Z
Axiom ( ρ ẋ dv ) =
·
ρ b dv + t da
B B ∂B

global statements

reference Z
placement [ Div P + ρ0 ( b − ẍ ) ] dV = o
B0

actual Z
placement [ div σ + ρ ( b − ẍ ) ] dv = o
B

Z Z
∂( ρ ẋ )
( − ρ b ) dv = ( σ − ρ ẋ ⊗ ẋ ) n da
∂t
B ∂B

local statements

reference
placement Div P + ρ0 ( b − ẍ ) = o

actual
placement div σ + ρ ( b − ẍ ) = o

∂( ρ ẋ )
− div( σ − ρ ẋ ⊗ ẋ ) − ρ b = o
∂t

11
1.3 Balance of moment of momentum

For non-polar bodies the axiom of the balance of moment (angular) momentum
reads
ḣ(0) = m(0) , (1.32)
where
Z
h(0) = x × ρ ẋ dv ,
B
Z Z Z Z (1.33)
m(0) = x × ρ b dv + x × t da = x × ρ b dv + x × σ n da
B ∂B B ∂B

are the moment of momentum with respect to a fixed reference point (0) of
the configuration space and the momentum of external forces with respect to
the same reference point.

With the material time derivative of h(0) ,

Z Z Z
ḣ(0) = ( x × ρ ẋ dv ) = ( x × ρ ẋ J dV ) =
· ·
( x × ρ J ẋ )· dV
B B0 B0
Z
= [ ẋ × ρ J ẋ + x × ( ρ J ẋ )· ] dV
B0
Z
= [ ẋ × ρ J ẋ + x × ( ρ̇ J ẋ + ρ J̇ ẋ + ρ J ẍ ) ] dV
B0
Z
= { ẋ × ρ J ẋ + x × [ ρ̇ J ẋ + ρ J ( div ẋ ) ẋ + ρ J ẍ ] } dV (1.34)
B0
Z
= { ẋ × ρ ẋ + x × [ ρ̇ ẋ + ρ ( div ẋ ) ẋ + ρ ẍ ] } J dV
B0
Z
= { ẋ × ρ ẋ + x × [ ( ρ̇ + ρ div ẋ ) ẋ + ρ ẍ ] } dv
| {z } | {z }
B = o = o
Z
= x × ρ ẍ dv ,
B

12
and the divergence theorem
Z Z
x × σ n da = ( x × div σ + I × σ ) dv (1.35)
∂B B
the balance of moment of momentum can be transferred to
Z Z Z
x × ρ ẍ dv = x × ρ b dv + ( x × div σ + I × σ ) dv
B B B
→
Z Z
x × ρ ẍ dv = [ x × ( div σ + ρ b ) + I × σ ] dv
B B
=⇒
Z
{ x × [ div σ + ρ ( b − ẍ ) ] + I × σ } dv = o . (1.36)
B
Considering the local statement of the balance of momentum,

div σ + ρ ( b − ẍ ) = o , (1.37)

the balance of moment of monmentum simplifies to

Z
I × σ dv = o . (1.38)
B

Thus, the local statement of the balance equation reads:

I×σ = o . (1.39)

The aformentioned equation is fulfill if

σ = (σ)T , (1.40)

i.e. the Cauchy stress tensor is symmetric.

13
 Summary: Balance of moment of momentum

Z Z Z
Axiom ( x × ρ ẋ dv ) =
·
x × ρ b dv + x × t da
B B ∂B

global statements

reference
placement

actual Z
placement I × σ dv = o
B

local statements

reference
placement

actual
placement I × σ = o =⇒ σ = (σ)T

14
1.4 Balance of energy (first law of thermodynamic)

For the description of thermo-mechanical effects, the balance of energy is of

main interest regarding the coupling of thermal fields (temperature, heat flux,
internal heat source) and mechanical fields (motion, velocity, acceleration, de-
formations, deformation velocities). The axiom of the balance of energy (first
law of thermodynamic) reads:
Ė + K̇ = W + Q . (1.41)
The scalar quantities
Z
E = ρ ε dv ,
B
Z
1
K = ρ ẋ · ẋ dv ,
2
B
Z Z Z Z
W = ẋ · ρ b dv + ẋ · t da = ẋ · ρ b dv + ẋ · σ n da (1.42)
B ∂B B ∂B
Z Z
= ẋ · ρ b dv + ẋ · σ da ,
B ∂B
Z Z Z Z
Q = ρ r dv − q · n da = ρ r dv − q · da
B ∂B B ∂B

denote the internal energy (E), where ε is the specific internal energy, the
kinetic energy (K), the increment of the mechanical work of the external forces
(W) and the increment of the non-mechanical work Q. The non-mechanical
work Q consists of two parts caused by the local external heat supply r = r(x, t)
per mass element ρ dv and the heat influx vector q = q(x, t).

With the material time derivations

Z Z
Ė = ( ρ ε dv ) =
·
( ρ ε J )· dV
B B0
Z (1.43)
= ( ρ̇ ε J + ρ ε̇ J + ρ ε J̇ ) dV
B0

15
 Z
= ( ρ̇ ε J + ρ ε̇ J + ρ ε J div ẋ ) dV
B0
Z Z
= ( ρ ε̇ + ε ( ρ̇ + ρ div ẋ ) dv = ρ ε̇ dv ,
| {z }
B = 0 B
Z Z
1 1
K̇ = ( ρ ẋ · ẋ dv )· = ( ρ J ẋ · ẋ )· dV
2 2
B B0
Z
1
= ( ρ̇ J ẋ · ẋ + ρ J̇ ẋ · ẋ + ρ J ẍ · ẋ + ρ J ẋ · ẍ ) dV (1.43)
2
B0
Z
1
= ( ρ̇ J ẋ · ẋ + ρ J ẋ · ẋ div ẋ + 2 ρ J ẋ · ẍ ) dV
2
B0
Z
1
= ( ρ̇ ẋ · ẋ + ρ ẋ · ẋ div ẋ + 2 ẋ · ẍ ) dv
2
B
Z Z
1
= [ ẋ · ẋ ( ρ̇ + ρ div ẋ ) + 2 ρ ẋ · ẍ ] dv = ρ ẋ · ẍ dv
2 | {z }
B = 0 B

and the relations

Z Z Z
T
ẋ · σ da = σ ẋ · da = div( σ T ẋ ) dv
∂B ∂B B
Z
= ( div σ · ẋ + σ · grad ẋ ) dv
B
Z (1.44)
= ( div σ · ẋ + σ · L ) dv ,
B
Z Z
q · da = div q dv
∂B B

the balance of energy (1.41) can be transferred to

16
 Z Z
ρ ε̇ dv + ρ ẍ · ẋ dv =
B B
Z Z (1.45)
= [ ( div σ + ρ b ) · ẋ + σ · L ] dv + ( ρ r − div q ) dv .
B B

Thus, the local statement of the balance of energy reads

ρ ε̇ = [ div σ + ρ ( b − ẍ ) ] · ẋ + σ · L + ρ r − div q . (1.46)

Considering the local statement of the balance of momentum,

div σ + ρ ( b − ẍ ) = o ,

see (1.23), one obtains the following representation form:

ρ ε̇ − σ · L − ρ r + div q = 0 . (1.47)

Figure 1.1: Illustration of heat flux and internal heat source

Taking into account the symmetric characteristic of the stress tensor σ = σ T

and the additive decomposition of L = D + W into a symmetric and a non-
symmetric part (D = DT , W = −WT ), the scalar product σ · L in (1.47)
results in

17
 σ · L = σ · ( D + W ) = σ · D + |σ {z · W} = σ · D .
(1.48)
= 0
Thus, one obtains the following statement of the balance of energy:

ρ ε̇ − σ · D − ρ r + div q = 0 . (1.49)

The introduction of the Helmholtz free energy function ψ = ψ(x, t),

ψ = ε − Θη , (1.50)

and the corresponding material time derivative,

ψ̇ = ε̇ − Θ̇ η − Θ η̇ , (1.51)

yields the alternative form

ρ ( ψ̇ + Θ̇ η + Θ η̇ ) − σ · D − ρ r + div q = 0 (1.52)

of the local balance of energy. The quantities η = η(x, t) and Θ = Θ(x, t) are
the specific entropy and the absolute temperature.

18
 Summary: Balance of energy

Z Z
1
Axiom ( ρ ε dv ) + (
·
ρ ẋ · ẋ dv )· =
2
B B
Z Z Z Z
= ẋ · ρ b dv + ẋ · t da + ρ r dv − q · n da
B ∂B B ∂B

global statements

actual Z Z
placement ρ ε̇ dv + ρ ẍ · ẋ dv =
B B
Z Z
= [ ( div σ + ρ b ) · ẋ + σ · L ] dv + ( ρ r − div q ) dv
B B

Z Z Z
ρ ε̇ dv = σ · D dv + ( ρ r − div q ) dv
B B B

local statements

actual
placement ρ ε̇ − σ · D − ρ r + div q = 0

ρ ( ψ̇ + Θ̇ η + Θ η̇ ) − σ · D − ρ r + div q = 0

19
Remark:
The kinetic energy of a body can be transformed into potential energy and
backwards. In this case it is a matter of purely mechanical conversion of
energy.

The kinetic energy can not disappear, but the energy distributes to the atoms,
i.e. the kinetic energy of the disordered motion of atoms can be transformed
into potential energy between the atoms. One can not see this energy. There-
fore, one says the kinetic energy is transformed into internal energy. This
energy can be felt and measured as heat. The temperature is a quantity for
the (medial) kinetic energy of the atoms.

Contributions of the internal energy:

– kinetic energy of molecules (see example),
– potential energy of molecules
(liquid or vapor expand
⇒ increasing distance of the molecules ⇒ evaporation),
– chemically bond energy of molecules.

20
1.4.1 Balance of energy – alternative representation forms

As aforementioned, the axiom of the balance of energy (first law of thermody-

namics) reads:

Ė + K̇ = W + Q , (1.53)

where
Z
E = ρ ε dv ,
B
Z
1
K = ρ ẋ · ẋ dv ,
2
B
Z Z Z Z (1.54)
W = ẋ · ρ b dv + ẋ · t da = ẋ · ρ b dv + ẋ · σ n da ,
B ∂B B ∂B
Z Z
Q = ρ r dv − q · n da .
B ∂B

Taking into account the balance equation of mass, the material time derivatives
of the internal and kinetic energy E and K are given by
Z Z
Ė = ( ρ ε dv ) =·
ρ ε̇ dv ,
B B
Z Z (1.55)
1
K̇ = ( ρ ẋ · ẋ dv )· = ρ ẋ · ẍ dv .
2
B B

With
Z Z
ẋ · σ n da = ( div σ · ẋ + σ · L ) dv (1.56)
∂B B
and the local statements of the balance of momentum and balance of moment
of momentum (symmetric characteristic of the stress tensor σ = σ T ) the rate
of the mechanical work W ca be reformulated:

21
 Z Z
W = ẋ · ρ b dv + ( div σ · ẋ + σ · D ) dv
B B
Z
= [ ( div σ + ρ b ) · ẋ + σ · D ] dv
| {z } (1.57)
B = ρ ẍ
Z Z
= ( ρ ẍ · ẋ + σ · D ) dv = ( ρ ẍ · ẋ ) dv + Win .
B B

The quantityZ
Win = σ · D dv (1.58)
B
denotes the rate of the internal mechanical work. With the additive decom-
position of the stress tensor σ and the symmetric part of the spatial velocity
gradient D into deviatorical and spherical parts,
1 1
σ = σD + ( σ · I ) I = σD − p I , p = − ( σ · I ) ,
3 3
(1.59)
1
D = DD + ( D · I ) I ,
3
and the relation (. . . )D ·I = 0, the rate of the mechanical work can be expressed
as
Z Z
1
W = σ · D dv = [ σ D − p I ] · [ DD + ( D · I ) I ] dv
3
B B
Z
1
= [ σ D · DD − p ( DD · I ) + ( σ D · I ) ( D · I ) −
| {z } 3 | {z }
B = 0 = 0
1
− p ( D · I ) ( I · I ) ] dv
3 | {z }
= 3 (1.60)
Z
= (σ D · DD − p D · I ) dv
B
Z
= ( σ D · DD − p div ẋ ) dv
B
Z
= ( σ D · DD − p J−1 J̇ ) dv .
B

22
With help of
Z Z
q · n da = div q dv (1.61)
∂B B
the rate of the non-mechanical work can be presented as
Z
Q = ( ρ r − div q ) dv . (1.62)
B

With the details mentioned before, one obtains the following global statement
of the balance of energy:
Z Z
Ė + K̇ = ρ ε̇ dv + ρ ẍ · ẋ dv
B B
Z Z
= ( ρ ẍ · ẋ + σ D D
· D − pJ
−1
J̇ ) dv + ( ρ r − div q(1.63)
) dv
B B

= W +Q .

Thus, the material time derivative of the internal energy reads:

Z
Ė = ρ ε̇ dv = W + Q − K̇
B
Z
= ρ ε̇ dv
B (1.64)
Z Z
= ( σ D · DD − p J−1 J̇ ) dv + ( ρ r − div q ) dv
B B

= Win + Q .

23
1.4.2 Balance of energy for gas and non-viscous fluids

With respect to the description of the behavior of gas and non-viscous fluids
the deviatorical part of the stresses can be approximately neglected, i.e.

σD = 0 . (1.65)

In this case, the expression for the rate of the internal work results in
Z Z
Win = − p J−1 J̇ dv = − p J̇ dV , (1.66)
B B0

where regarding the second term the transport theorem dv = JdV has been
used. With the assumption that the pressure is constant in space one obtains
Z Z Z
Win = − p J̇ dV = − p ( J dV ) = − p ( dv )·
·

B0 B0 B (1.67)
dv
= − p V̇ = − p .
dt
Insertion this relation into the expression for Ė yields:

Ė = Win + Q = − p V̇ + Q . (1.68)

24
1.5 Entropy inequality (second law of thermodynamics)

The entropy is a measure of a part of heat quantity which can not transformed
into mechanical work due to the equal distributions of the molecules of the sys-
tem. Thus, the entropy inequality (second law of thermodynamics) is defined
as follows
Z Z
1 1
Ḣ ≥ ρ r dv − q · n da , (1.69)
Θ Θ
B ∂B
where
Z
H = ρ η dv (1.70)
B
denote the entropy and η the specific entropy. Considering the materiel time
derivatives
Z Z
Ḣ = ( ρ η dv ) =
·
( ρ η J )· dv
B B0
Z
= ( ρ̇ η J + ρ η̇ J + ρ η J̇ ) dv
B0
Z (1.71)
= ( ρ̇ η J + ρ η̇ J + ρ η J div ẋ ) dv
B0
Z Z
= [ ρ η̇ + η ( ρ̇ + ρ div ẋ ) ] dv = ρ η̇ dv
| {z }
B = 0 B

and the relation

Z Z
1 1
q · n da = div( q ) dv (1.72)
Θ Θ
∂B B
the entropy inequality results in
Z Z
1 1
ρ η̇ dv ≥ [ ρ r − div ( q ) ] dv . (1.73)
Θ Θ
B B

With help of (1.73), the local statement

25
 1 1
ρ η̇ − ρ r + div ( q ) ≥ 0 . (1.74)
Θ Θ
is gained. Using the relation
1 1 1
div ( q ) = − 2 grad Θ · q + div q (1.75)
Θ Θ Θ
one obtains the following form of the second law of thermodynamics:
1 1
ρ η̇ − ( ρ r − div q ) − 2 q · grad Θ ≥ 0 . (1.76)
Θ Θ
Taking into account the balance of energy, see (1.49),

ρ ε̇ − σ · D − ρ r + div q = 0

and

ρ r − div q = ρ ε̇ − σ · D ,

respectively one obtains the following representation form of the inequality

(1.76):
1 1
ρ η̇ − ( ρ ε̇ − σ · D ) − 2 q · grad Θ ≥ 0 . (1.77)
Θ Θ
The multiplication of the aforementioned inequality with Θ (regarding the
absolute temperature it is essential: Θ ≥ 0) yields
1
Θ ρ η̇ − ρ ε̇ + σ · D − q · grad Θ ≥ 0
Θ
=⇒
1
− ρ ( ε̇ − Θ η̇ ) + σ · D − q · grad Θ ≥ 0 . (1.78)
Θ

The inequality (1.78) can be reformulated as follows:

1
− ρ ( ε̇ − Θ η̇ − Θ̇ η + Θ̇ η ) + σ · D − q · grad Θ ≥ 0
Θ
=⇒
1
− ρ [ ( ε − Θ η )· + Θ̇ η ] + σ · D − q · grad Θ ≥ 0 . (1.79)
Θ

26
The expression ( ε − Θ η )· represents a total differential. Thus, these quantities
in the brackets can be combined to one quantity. This quantity

ψ = ε − Θη (1.80)

is called as Helmholtz free energy, compare (1.50). Finally, with (1.80) the
local statement
1
− ρ ( ψ̇ + Θ̇ η ) + σ · D − q · grad Θ ≥ 0 . (1.81)
Θ
of the entropy inequality can be derived.

Special cases:
For processes with constant temperature in space, the global statement of the
second law of thermodynamics, see (1.69) and (1.73), respectively the global
statement of the second law of thermodynamics simplifies to
Z Z
1
ρ η̇ dv ≥ ( ρ r − div q ) dv (1.82)
Θ
B B
and
1
Ḣ ≥ Q , (1.83)
Θ
respectively, where (1.62) has taken into consideration. This relation is the
starting point regarding the formulation of the well-known Gibbs equation in
the framework of the gas dynamics.

Remark:
With respect to the derivation of the local statement (1.52) of the balance
of energy, the introduced relationship for the Helmholtz free energy funktion
ψ = ε−Θ η seemed arbitrary. The expression for ψ recently arises in connection
with the reformulation with the entropy inequality. The reformulation of the
entropy implies the change of variables, i.e. the substitution of the variable
set {ε, η} by the set {ψ, η}. The approach is called Legendre transformation.

27
 Summary: Entropy inequality

Z Z Z
1 1
Axiom ( ρ η dv ) ≥
·
ρ r dv − q · n da
Θ Θ
B B ∂B

global statement

actual Z Z
1 1
placement ρ η̇ dv ≥ [ ρ r − div ( q ) ] dv
Θ Θ
B B

local statement

actual
1 1
placement ρ η̇ − ρ r + div ( q ) ≥ 0
Θ Θ

1
− ρ ( ε̇ − Θ η̇ ) + σ · D − q · grad Θ ≥ 0
Θ

1
− ρ ( ψ̇ + Θ̇ η ) + σ · D − q · grad Θ ≥ 0
Θ

28