Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

2. Thermodynamics


2.1 The first law of thermodynamics

Thermodynamics concerns energy and the way that energy is transferred. The first law
of thermodynamics addresses the energy conservation. It says that the energy can
neither be created nor destroyed in a system of constant mass, although it may be
converted from one form to another.

The system exchanges energy with external environment by either changing its internal
energy or doing work to the environment. The internal energy is defined as the total
kinetic and potential energies of atoms and molecules. Suppose that Q amount of heat
is added to the system, the energy conservation gives

w U Q + = (2.1)

Where U is the change of internal energy and w is the work done by the system.

If Q
P
energy is introduced to the confined gas with constant pressure P, on the one side
the internal energy increases and on another side the gas is expanded to maintain the
constant pressure, as illustrated in figure 1.


Figure 1. Gas expansion due to energy absorption

During the volume expansion, gas has done work by pushing the piston. The work is
given by

V P w = (2.2)
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

where V is the change of volume. Substituting equation (2.2) into equation (2.1) gives

( ) PV U Q
P
+ =
(2.3)

The term U+PV is called enthalpy PV U H + = . When V=0, no work is done by the
system, equation (2.1) reduces into

U Q
V
=
(2.4)

where Q
V
is the energy absorbed by the system at constant volume condition.


2.2 The second law of thermodynamics

The second law of thermodynamics addresses the direction of reaction. Whether a
reaction can happen in a given direction depends on the so-called free energy.

Entropy is defined as


T
Q
dS

= (2.5)

It was found that the entropy of a closed system can decrease (irreversible reaction) or
stay constant (equilibrium).

The function which decides whether a process will occur is the free energy change, G,
where

S T V P U G + = (2.6)

if G<0 the reaction will go ahead. At constant pressure equation (2.6) changes into

S T H G = (2.7)

where G is known as the Gibbs energy change of the processing. At constant volume
equation (2.6) changes into
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)


S T U F = (2.8)

F is called the Helmholtz energy.

By the second law of the thermodynamics, one can judge which solidification is possible
when free energies of all possible phases are known. Figure 2 illustrates a schematic
free energy diagram for solidification. It can be see that liquid will change into solid a
when the temperature is below the melting point. The solid b can never be formed
because its free energy is always the highest.



Figure 2. Schematic diagram of free energy changes vs temperature.


2.3 Entropy of binary alloy

Entropy is defined as T Q S / = in thermodynamics, where Q is the amount of heat
absorbed or evolved in an isothermal and reversible process in which the system goes
from one state to another, and T is the absolute temperature at which the process is
occurring. 0 =

S when system passes through a series of reversible, equilibrium and

isothermal steps and arriving back to the initial state.

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

The thermodynamic definition of entropy is only valid for a system in equilibrium
(because temperature is defined only for a system in equilibrium), while statistical
definition of entropy applies to any system. Thus the statistical definition is usually
considered fundamental definition of entropy.

Kelvin and Boltzmann considered that the entropy is related to the probability of a
system by

W k S ln = (2.9)

where k=1.38x10
-23
J/K is Boltzmann constant and W is the possibility (a measure of
disorder). Equation (2.9) means that the maximum entropy is associated with the
greatest disorder. When the temperature of the system approached absolute zero the
entropy of the system would approach zero.

The 3
rd
law of thermodynamics: The entropy of a condensed system would be zero at
a temperature of absolute zero.

Alloy is solution which is made up of components. There is solubility between the
various components. For an alloy in which there is no repulsive and attractive
interactions between various components, atoms (or molecules) can be mixed up
ideally. Suppose that n atom or molecule of component A is mixed up with N-n number
of component B, the possibility is given by

)! ( !
!
n N n
N
W

= (2.10)

The possibility is demonstrated in figure 3 for a binary crystal (N=9, n=1).

Figure 3. Possibilities of atoms arrangement
Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

Inserting equation (2.10) into equation (2.9) gives the entropy

|
|

\
|

=
)! ( !
!
ln
n N n
N
k S (2.11)

Using Stirling approximation N N N N = ln ) ! ln( , equation (2.11) becomes

[ ]
(

\
|
+
|

\
|
=
=
N
n N
N
n N
N
n
N
n
Nk
n N n N n n N N k S
ln ln
) ln( ) ( ln ln
(2.12)

Let N n x
A
/ = and ( ) N n N x
B
/ = ,
A
x and
B
x are molar fraction of components A and B
in the solution. The molar entropy in ideal solution is

( )
B B A A
x x x x R S ln ln + = (2.13)

If there are no repulsive or attractive interactions between atoms A and B the solution is
called ideal and the Gibbs energy of mixing is given by

( )
B B A A
ideal
mix
x x x x RT G ln ln + = (2.14)

Generally, it takes the following format for multiple component solution

=
i
i i
ideal
mix
x x RT G ln (2.15)

where
i
x is the molar fraction of component i .

Normally there are interactions between different atoms or molecules of various
components. The excess mixing energy,
xs
mix
G , should be considered. The simplest way
to consider is via the regular solution model where

=
B A
xe
mix
x x G (2.16)

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

where is the regular solution interaction energy parameter and is related to the
energy of bonds between A and B atoms or molecules. >0 corresponds to repulsive
interaction, such as Cu-Ag. <0 corresponds to the attractive interaction, such as Fe-Ni.
The total Gibbs energy of binary alloy is given by combination of equations (2.14) and
(2.16).

More generally,
xs
mix
G is expressed as

[ ]

=
+
+ =
+ + + =
n
i
n
i j
j i ij j i ij ij j i
xe
mix
x x x x x x G
1
1
1
2 2 1 0
... ) ( ) ( (2.17)

The reference states should be added to the mixing Gibbs energy. The reference Gibbs
energy is

=
i
i i ref
G x G (2.18)

where

i
G is the Gibbs energy of the phase at pure i . The Gibbs energy of solution,
therefore, is expressed at

[ ]

=
+
+ =
+ + + + + =
n
i
n
i j
j i ij j i ij ij j i
i
i i
i
i i
x x x x x x x x RT G x G
1
1
1
2 2 1 0
... ) ( ) ( ln (2.19)

Equation (2.19) is plotted for a binary alloy with following parameters

RT=1
G
A
=0.05
G
B
=0.3

AB
0
=-2

AB
1
=
AB
2
==0

The result is the blue line in figure 4.

Graduate Institute of Ferrous Technology, POSTECH

Rongshan Qin (R. S. Qin)

-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0 0.2 0.4 0.6 0.8 1
MOLAR FRACTION B
G
I
B
B
S

M
I
X
I
N
G

E
N
E
R
G
Y
G-ideal
G-xe
G-mix
G


Figure 4. Gibbs energy

Solidification is a processing that the free energy goes to minimum at equilibrium.
Figure 5 shows the free energy minimization during solidification. In equilibrium, the
solute concentration in solid should be
E
S
x and in liquid should be
E
L
x .

Figure 5. Free energy minimization during solidification

References

1. M.C. Flemings, Solidification processing, 1974.
2. N. Saunders and A.P. Miodownik, CALPHAD, 1998.
3. A.T. Dinsdale, CALPHAD 15 (1991) 317.
Solid
Liquid
x
0

x
S
E

x
L
E